Liquid-phase fluorination

ABSTRACT

This invention pertains to a method for liquid phase fluorination for perfluorination of a wide variety of hydrogen-containing compounds.

This application is a Continuation Application of U.S. patentapplication Ser. No. 08/258,708 filed Jun. 13, 1994, which issued asU.S. Pat. No. 5,461,117 on Oct. 24, 1995, which is a ContinuationApplication of U.S. patent application Ser. No. 08/028,721, filed Mar.8, 1993, which issued as U.S. Pat. No. 5,322,904 on Jun. 21, 1994, whichis a Continuation-in-Part Application of U.S. patent application Ser.No. 07/823,837, filed Jan. 17, 1992, now abandoned, which is aContinuation Application of U.S. patent application Ser. No. 07/414,119,filed Sep. 28, 1989, which issued as U.S. Pat. No. 5,093,432 on Mar. 3,1992, which is a Continuation-in-Part Application of U.S. patentapplication Ser. No. 07/250,376, filed Sep. 28, 1988, now abandoned, theteachings of which are all incorporated by reference herein.

BACKGROUND OF THE INVENTION

Hydrocarbons can be converted to fluorocarbons in two commerciallyviable ways. Electrochemical fluorination (ECF) is widely used tofluorinate materials which are soluble and stable in liquid hydrogenfluoride (HF). Of among the classes of materials prepared in thismanner, perfluorotertiary amines and perfluorosulfonic acids are bestsuited for the technique giving yields generally in excess of 70%. Otherclasses of compounds such as carboxylic acids and their derivatives canbe fluorinated electrochemically; however, the yields are usually lowand have a tendency to decline rapidly as the number of carbons in themolecule is increased. In general, a very low yield (less than 25%) willbe obtained for any perfluorinated carboxylic acid containing over 12carbon atoms.

A second widely used process for preparing perfluorocarbons involvescontacting a hydrocarbon, in the gaseous form, with cobalt trifluoride.This technique, although narrow in applicability, works well for lowmolecular weight hydrocarbons, especially polyaromatic compounds whichare sufficiently volatile to allow vaporization. Examples of materialswhich can be fluorinated in this manner include decalin.tetradecahydrophenanthrene, naphthalene, decane, dodecane, etc.

Russell et al. (U.S. Pat. No. 3,897,502) describe a process whereby oneor several fluorine atoms can be added to a partially fluorinated lowmolecular weight hydrocarbon. The material to be treated is dissolved inan inert solvent through which dilute fluorine is bubbled at lowtemperatures (-10° C. to -30° C.). The resulting product is a partiallyfluorinated material which typically contains several additionalfluorine atoms. Scherer et al. (U.S. Pat. No. 4,686,024) teach a methodfor perfluorinating low molecular weight partially fluorinatedhydrocarbons. Highly fluorinated starting materials are slowly pumpedinto a fluorocarbon solvent over a 3 to 5 day period. As the organicmaterial is being delivered, a large excess of pure fluorine gas isbubbled through the solvent (typically a 5 to 8 fold excess). Anultraviolet lamp is used to activate the fluorine to produce theproducts of interest. The yields reported generally range from 20% to50% for materials which contain 3 to 5 hydrogens which must be replacedby fluorine. Calini et al. (European Patent Application 269,029)describe a fluorination process in which a hydrogenated ether compoundis reacted with F₂ diluted with an inert gas in a liquid phase, in thepresence of an alkali metal fluoride.

SUMMARY OF THE INVENTION

This invention pertains to liquid phase fluorination for perfluorinationof a wide variety of hydrogen-containing compounds. The fluorination isperformed in a perhalogenated liquid medium, such as a perfluorocarbonmedium, a perhalogenated chlorofluorocarbon medium or a perhalogenatedchlorofluoroether. The hydrogen-containing compound is introduced intothe medium while the medium is agitated so that the compound isdissolved or dispersed within the medium in order to prevent substantialoligomerization and/or polymerization of the hydrogen-containingcompound upon fluorination. Fluorine gas, diluted with an inert gas, isthen introduced into the medium to fluorinate the hydrogen-containingcompound. The fluorine is diluted so that it is below the flammablelimits of the liquid medium (in fluorine). The fluorine is introduced inan amount in excess of the stoichiometric amount needed to replace allof the hydrogen atoms of the hydrogen-containing compound. Thetemperature is maintained above the melting point of the solvent, belowthe temperature at which fluorine reacts with the liquid and below thetemperature in which fragmentation of the hydrogen-containing compoundoccurs. The fluorination is carried out in the absence of ultravioletlight and continued (as a batch or continuous process) until all thehydrogen-containing compound is introduced into the liquid medium andfluorinated, wherein there is substantially no concurrentoligomerization and/or polymerization of the perfluorinated compound.

It has been found, in accordance with the present invention, that a widevariety of hydrogen-containing compounds can be fluorinated using theliquid phase fluorination. The method of the invention can be used toprepare fluorinated products which can be prepared by ECF and cobalttrifluoride processes as well as products such as perfluoropolyethers,high molecular weight fluorocarbon diacids, and high molecular weighthydrocarbons which cannot be prepared by the existing fluorinationtechnologies. The fluorinated products can be obtained typically inhigher yield and in purer form than in other processes.

The mild conditions employed in the method of this invention make itpossible to preserve chemical functionalities on a fluorinated molecule.For example, chlorinated hydrocarbons can be converted topolyfluorinated materials with essentially all of the chlorine beingretained in original positions. Polyesters and acyl fluorides can beconverted to perfluorocarbons with essentially complete retention of theester functionality. Perfluoro-tertiary amines, sulfonic acids, sulfonicesters and ketones can all be prepared in high yield.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of a liquid phase fluorinationreactor.

FIG. 2 is a schematic representation of another liquid phasefluorination reactor.

DETAILED DESCRIPTION OF THE INVENTION

The perfluorination reactions are carried out in a liquid phasefluorination reactor. A suitable reactor is shown schematically inFIG. 1. The reactor consists of a reaction vessel equipped with a meansfor agitating vigorously a liquid contained therein (a stirrer), a meansof removing the heat (internal or external cooling coils, a constanttemperature bath, etc.), a fluorine inlet, an inlet line for introducingthe hydrogen-containing compound to be fluorinated, a gas outlet line, acondenser for condensing vaporized liquid from the reaction vessel and aliquid return line for returning condensed liquid back into the reactionvessel. Downstream from the reactor a hydrogen fluoride scrubber (suchas a sodium fluoride-filled tube), instrumentation for measuring thefluorine concentration in the off gas (which can be donetitrametrically, with an ion specific electrode, calorimetrically, etc.)and a fluorine scrubber (such as a tube filled with alumina, sulfur,etc.) are installed.

Liquid perhalogenated chlorofluorocarbons, chlorofluoroethers andperfluorocarbons serve as useful liquid phase medium in the fluorinationreaction. Collectively, these compounds are referred to herein as theperhalogenated liquid fluorination medium. Examples of some suchchlorofluoroethers are:

    (CF.sub.2 Cl).sub.2 CFOCF.sub.2 OCF(CF.sub.2 Cl).sub.2

    CF.sub.2 ClCF.sub.2 OCF.sub.2 OCF.sub.2 CF.sub.2 Cl

When perfluorinating low molecular weight polyethers, it is preferrablethat the liquid fluorination medium be the same as the fluorinationproduct of the reaction. This eliminates the need to separate thefluorinated product from the liquid medium.

According to the method of the invention, the fluorination reaction iscarried out by placing a perhalogenated liquid in the reactor, such as aperfluorocarbon, a perhalogenated chlorofluorocarbon or a perhalogenatedchlorofluoroether. For clarity, the following description pertains to1,1,2-trichlorotrifluoroethane which is a useful solvent for mostreactions; however, as pointed out above, other perhalogenatedchlorofluorocarbons or perfluorocarbons, such as Fluorinert FC-75described in Example 70, may be used.

Before beginning the reaction, the reactor is purged of air, generally,by flushing the reactor with inert gas such as nitrogen gas forapproximately 30 minutes. The reactor temperature is adjusted to thedesired temperature, i,e. a temperature high enough for the fluorinationreaction to occur but low enough to prevent fragmentation of thehydrogen-containing compound, usually between -40° C. and +150° C.,preferably between -10° C. and +50° C. Similarly, the condenser iscooled to its operating temperature (typically -35° C.). Thehydrogen-containing material to be fluorinated is introduced into thereactor at a controlled rate as fluorine gas and a diluent inert gas(e.g. nitrogen), are introduced therein. Preferably, the fluorine isbubbled through the vigorously agitated perhalogenated liquidfluorination medium but it may also be introduced into the vapor spaceof the reactor. The perhalogenated liquid fluorination medium isagitated so that the hydrogen-containing compound is dissolved ordispersed within the liquid medium in order to prevent substantialoligomerization and/or polymerization of the hydrogen-containingcompound upon fluorination. The fluorine is introduced at a rateslightly above that required to theoretically replace all of thehydrogen atoms present on the molecule to be fluorinated (typically a10% to 40% excess of fluorine is used). The fluorination reaction iscarried out in the absence of ultraviolet light.

Upon completing the addition of the hydrogen-containing material, thefluorine concentration in the gas exit line typically increases sharply,denoting the end of the fluorination reaction. However, in the case ofhigh molecular weight polymers (5,000 to 30,000 amu) and hydrocarbonswhich are either insoluble or sparingly soluble in the liquid, it isoften beneficial to slowly meter into the reactor a small amount of alow molecular weight hydrocarbon such as benzene after adding thehydrogen-containing compound to be fluorinated to ensureperfluorination. The hydrocarbon reacts with the fluorine producing anabundance of fluorine radicals which are highly reactive and replace thelast remaining hydrogen atoms on the product.

The hydrogen-containing compound to be fluorinated can be metered intothe reactor neat if it has a sufficiently low viscosity (less than about50 cst. at 100° F.), or it may be diluted with a solvent. Normally, thesolvent is the fluorination liquid. For example, if1,1,2-trichlorotrifluoroethane is used as the liquid fluorinationmedium, the material to be fluorinated is typically diluted with1,1,2-trichlorotrifluoroethane before being introduced into the reactor.With high molecular weight polymers which are often solids, the dilutionbecomes very important.

If the hydrogen-containing compound is insoluble in the perhalogenatedliquid fluorination medium, it can still be fluorinated in high yield byforming an emulsion with the liquid fluorination medium. One convenientway of preparing such compounds involves preparing the emulsioncontinuously in situ as the fluorination reaction proceeds. For example,if 1,1,2-trichlorotrifluoroethane is used as the fluorination liquid,the hydrogen-containing compound is first diluted with a suitablesolvent which has a high solvating power and at the same time willconsume little if any of the fluorine. Chloroform, trichloroethene,trichloroethane, trifluoroacetic acid or trifluoroacetic anhydride canusually be used as the solvent. Upon dissolving the hydrogen-containingcompound in the solvent, 1,1,2-trichlorotrifluoroethane is then addedslowly until the reactant solution becomes cloudy, signifying that thehydrogen-containing compound is beginning to precipitate or becomeimmiscible with the solvent mixture. The hydrogen-containingcompound/1,1,2-trichlorotrifluoroethane/solvent mixture is then slowlypumped into the fluorination reactor in the usual manner, as previouslydescribed. As the solution contacts the perhalogenated liquidfluorination medium, a fine emulsion or precipitate is formed dependingupon the nature of the hydrogen-containing compound. The solution,although heterogeneous, allows for fluorination as though it washomogeneous owing to the very small particle size of the suspendedmaterial.

The fluorine gas is diluted with an inert gas such as nitrogen. This isof particular importance if a fluorination medium such as1,1,2-trichlorotrifluoroethane is used. It is imperative to keep thefluorine concentration low so that the perhalogenated liquidfluorination medium and fluorine in the vapor space do not form aflammable mixture. The flammability limits of various solvents influorine gas can be determined by spark testing. In a typical reaction,a fluorine concentration of 10 to 40% in 1,1,2-trichlorotrifluoroethaneworks well. If operating properly, the fluorine concentration in theexit gas will be between 2 and 4%.

The continuous addition reactor may be operated in a batch or continuousmode. If operating continuously, a small portion of the reactor contentsis removed continuously or periodically. The product is recovered bydistillation or other means and the liquid fluorination medium isreturned to the reactor.

Sodium fluoride or other hydrogen fluoride scavengers, (see U.S. Pat.No. 4,755,567) may be present in the solution to scavenge the by-producthydrogen fluoride. The preferred mode for carrying out the reaction formany polyethers is with a sufficient quantity of sodium fluoride beingpresent to complex with all of the hydrogen fluoride formed during thefluorination. When fluorinating ethers in the presence of sodiumfluoride, improved yields are obtained while chain cleavage andrearrangements are minimized.

Polyethers containing sterically hindered oxygens and/or chlorine in thevicinity of the oxygen can be fluorinated in high yield without having ahydrogen fluoride scavenger present. Naturally, these reactions are moreamenable to continuous processes than those reactions requiring ahydrogen fluoride scavenger.

The method of this invention is extremely versatile and allowsfluorination of many different classes of hydrogen-containing materials,including ethers and polyethers having 5 to 10,000 carbon atoms. Cyclicethers having more than 10 carbon atoms can also be fluorinated by themethods of this invention. This method allows the perfluorination of thehydrogen-containing materials without substantial concurrentoligomerization and/or polymerization. Oligomerization is considered tobe the formation in substantial amounts of byproducts that are moleculesthat have only a few monomer units. Similarly, polymerization is definedas the formation in substantial amounts as byproducts of any substancewhich has a molecular structure made up largely or completely from anumber of similar monomer units bonded together. To illustrate this, thefluorination of several classes of compounds is described below.

Production of Perfluorinated Acids and Their Derivatives

Perfluorinated acids such as C₇ F₁₅ COOH and their derivatives havereceived much attention through the last forty years principally becausemany products of commercial value such as oil- and water-repellantfinishes for textile and paper, stain-repellant finishes for leather,surfactants for a variety of applications and other commercial productsare based on perfluorinated acids and their derivatives. Perfluorinatedacids are made primarily by two methods. The first method involveselectrochemical fluorination (ECF) of acid derivatives to perfluorinatedacid derivatives. The second main method involves the use of telomersmade from perfluoroiodoalkanes and tetrafluoroethylene in multi-steproutes. For a discussion of how perfluorinated acid derivatives are madesee, for example, R. E. Banks, ed., Preparation, Properties andIndustrial Applications of Organofluorine Compounds, Chapter 1, JohnWiley & Sons, 1982.

In ECF of acid derivatives, the yield of perfluoro acid produced fallsof rapidly with increasing chain length of the feed stock. The effect ofmolecular weight on the yield is best illustrated by the followingreaction (1): ##STR1## n=6, 16% yield; n=7, 10% yield; n=11, 0.5% yield.An important contributing factor for the low yields is the formation ofcyclic perfluoropolyethers when n=3. For example, a major by-product ofperfluorooctanoic acid production isperfluoro-(2-n-butyltetrahydrofuran). Other by-products include tars andfragmentation products. The formation of by-products in ECF reactions ofacid derivatives makes it difficult if not impossible to make materialssuch as some of the long chain diacids described in the examples whichfollow.

With the liquid phase fluorination techniques of this invention, it ispossible to make a wide variety of perfluorinated acids and acidderivatives in very high yields. In many cases there is practically noloss of functional groups and there are very few side reactions.

The hydrogen-containing starting material can be reacted with fluorinein a reactor such as the one just described and shown in the schematicof FIG. 1. There are a variety of acid derivatives that can be reacted.Organic acids themselves are generally not a good choice. For example,the fluorination of decanoic acid gives perfluorononap, in high yield asthe product decarboxylates during the fluorination. Although decanol canbe used as a reactant to produce mainly perfluorodecanoic acid, apotential by-product of this reaction is a hypofluoride so it may not bethe reactant of choice. Acid halides work very well as organicreactants. Using decanoyl fluoride, perfluorodecanoic acid can be madein high yields. However, when decanoyl chloride is used as the reactant,a considerable amount of chlorine substitution on the product results.With decanoyl chloride, the resulting product after hydrolysis containsa material where about 50% of the molecules have one or more chlorinesin the molecule (i.e. C₉ F₁₈ ClCOOH). Another disadvantage of using acidhalides is that they must be handled under anhydrous conditions as theywill easily hydrolyze to form acids which decarboxylate during thefluorination. However, the use of acid fluorides might be the preferredfeedstock choice in a production facility as the least amount ofelemental fluoride is needed. For laboratory-scale reactions, esters areprobably the reactant of choice. With primary esters, both ends of theester group are converted to perfluoro acids after fluorination followedby hydrolysis. For example, the hydrolysis of one mole ofperfluoro(octanoyl octanoate), gives two moles of perfluoro octanoicacid. Using octanoyl acetate, one mole of perfluorooctanoic acid and onemole of trifluoroacetic acid is made. As can be seen from the reactionsbelow: ##STR2## slightly more fluorine is required to fluorinate anester than the corresponding acid fluoride to make the same product.However, the hydrocarbon esters are stable in air and can be handled inglass equipment. In a production facility, it may be more cost effectiveto use acid fluorides since the main cost of products would probably beassociated with the cost of fluorine gas.

When secondary alcohols or esters of secondary alcohols are reactedusing this invention, the resulting product after hydrolysis is aperfluoroketone. For example, the hydrolysis of perfluoro(isopropyloctanoate) yields perfluorooctanoic acid and hexafluoroacetone afterhydrolysis. 2-Octanol yields perfluoro-2-octanone and acetyl-2-octanoateyields trifluoroacetic acid and perfluoro-2-octanone after hydrolysis.These reactions are shown as follows: ##STR3##

When tertiary alcohols are reacted according to this invention, tertiaryalcohols are produced in low yields with mostly perfluoroalkanes beingproduced. However, esters of tertiary alcohols give fair yields oftertiary perfluoro alcohols after hydrolysis.

There are many applications in the aerospace and related industries, inwhich, o-rings, gaskets and sealants are needed which can withstand hightemperatures while also exhibiting good low-temperature flexibility. Themethylol-terminated prepolymers which can be made by reduction ofperfluorocarbon diacids and described in several of the followingexamples are promising precursors for such materials. For example,polyurethanes can be prepared by reacting hydroxyl-terminatedfluorocarbons with aromatic diisocyanates. Similarly, useful binders canbe prepared by reacting the methylol-terminated fluorocarbon withparaformaldehyde.

Production of Perfluorinated Ethers

An important class of materials that can be produced using the liquidphase fluorination techniques of this invention are perfluoroethers andpolyethers. The production of perfluoropolyethers by ECF or cobalttrifluoride fluorination has not resulted in commercially viableprocesses due to extensive fragmentation reactions which usually occur.Methods have been developed for making perfluoropolyethers by directfluorination (see, for example, U.S. Pat. No. 3,775,489). Liquid-phasefluorination provides a process capable of producing better quality(e.g., higher linearity) perfluoropolyethers having higher yields.

Hydrocarbon ethers such as polyethers are more difficult to prepare bydirect fluorination than other hydrocarbons due to their sensitivity tothe by-product hydrogen fluoride generated in the process. Hydrogenfluoride has a tendency to cause acid cleavage of the ether linkages.The degree of sensitivity varies greatly with the structure of theether. Linear polyethers containing a low carbon to oxygen ratio aremost reactive while polyethers containing some chlorine and fluorinesubstituents are remarkably stable in the presence of hydrogen fluoride.In spite of this, virtually all ethers can be prepared by the method ofthis invention in excellent yields if provisions are taken to minimizethe exposure of the ether to the hydrogen fluoride. A variety oftechniques can be used to accomplish this. For example, sodium fluoridecan be charged into the reactor along with the fluorination liquid. Thesodium fluoride slurry scavenges the hydrogen fluoride to give sodiumbifluoride.

A slight modification of this approach which works well involves placingsodium fluoride pellets in a second vessel through which the gaseousproducts of the reaction are passed. For this approach, the reactorshown in FIG. 2 can be used. A gas pump is used to circulate the gasesin the reactor through the sodium fluoride bed (which removes thehydrogen fluoride) and then to reinject the gases, which containunreacted fluorine, back into the reactor. By isolating the sodiumfluoride from the product, the recovery of the product is greatlysimplified and the process can be made continuous by employing severalsodium fluoride beds which can alternately be regenerated by heating.

An alternate approach which gives satisfactory results involves using aperhalogenated liquid fluorination medium with a boiling point highenough to allow the fluorination reaction to be carried out at asufficiently high temperature to allow the by-product hydrogen fluorideto be quickly removed from the reactor. This greatly facilitates theremoval of hydrogen fluoride because the solubility of hydrogen fluoridein the liquid phase decreases with increasing temperature. Typically, aperhalogenated liquid fluorination medium having a boiling point near100° C. works well. Thus, it is often possible to prepareperfluoropolyethers in high yield without using a hydrogen fluoridescavenger.

A slight variation of this approach involves placing a sodium fluoridetrap in the liquid return line between the condenser and the reactor.The majority of the hydrogen fluoride is swept from the reactor and iscondensed in the condenser along with some of the fluorination liquid.The fluorination liquid is phase separated from the hydrogen fluorideand is returned to the reactor. By placing a sodium fluoride trap in theliquid return line, one can be certain that the liquid returning to thereactor is free of hydrogen fluoride.

Production of Other Fluorochemicals

There are a wide variety of other fluorochemicals that can be made usingthis invention. Classes of materials that can be fluorinated includealkanes, alkenes, aromatic hydrocarbons, sulfonic acid derivatives,amines, chlorinated hydrocarbons, carboxylic acid derivatives, ethers,formals, acetals, ketals, epoxides and others.

Perhalogenated acetals, ketals and formals are described in U.S. patentapplication Ser. No. 07/250,384, filed Sep. 28, 1988, now abandoned andU.S. Pat. No. 5,053,536, issued to Bierschenk et al., Mar. 3, 1992.Perhalogenation of epoxides is described in U.S. patent application Ser.No. 07/251,135, filed Sep. 28, 1988, now abandoned and Ser. No.07/414,134, now abandoned. The teachings of each of these applicationsare incorporated by reference herein.

Both large and small molecules can be reacted using this invention toyield products ranging from single compounds to polymers. Alkanes andalkenes are generally quite soluble in 1,1,2-trichlorotrifluoroethaneand similar solvents so they can easily be added either neat or insolution to the reactor. Materials such as perfluorokerosene are usefulas mass markers in mass spectrometry. It is also possible to produceunique materials such as elastomeric perfluoroethylene-propylenecopolymers using this invention. Hydrocarbon ethylene-propylenecopolymers can be produced with nearly any ratio of ethylene topropylene so it is possible to use this invention to produceperfluoroethylene-propylene copolymers with ethylene to propylene ratiosof about one to one which are elastomeric. If one uses perfluoroethyleneand perfluoropropylene monomers to produce perfluoroethylene-propylenecopolymers, the difference in monomer reactivity limits the amount ofhexafluoropropylene that can be incorporated in the polymer to a rangesuch that the polymer is not elastomeric. Aromatic and polyaromatichydrocarbons, such as phenanthrene or polystyrene, can also be reactedusing this invention with the aromatic groups becoming saturated withfluorine as the hydrogens are being replaced with fluorine. Preferably,mono and polycyclic aromatic compounds will have 6 to 30 carbon atoms.

Perfluoroamines can be made using this invention as well. Although someof the yields are relatively low due to the tendency to form tars atsome stage of the reaction, the addition of an acid such astrifluoroacetic acid to the hydrocarbon amine appears to improve theyield and the use of both a chlorofluorocarbon and liquid HF as theliquid phase in the reactor improves the yield even more.

Sulfonic acids and derivatives such as sulfonyl chlorides, sulfonylfluorides and alkyl sulfonates can be converted in high yields to giveperfluoroalkyl sulfonyl derivatives. Fluorocarbon sulfonyl derivativesoffer many advantages over conventional hydrocarbon surfactants. Theygive lower surface tensions, are more stable, show surface activity inorganic systems and exhibit both excellent water and oil repellancy.Although low molecular weight fluorocarbon sulfonic acid derivatives canbe prepared in the electrochemical cell, the fluorination of hydrocarbonsulfonyl derivatives in perhalogenated liquid fluorination mediumrepresents a superior means of preparing fluorocarbons having over sixto eight carbons. Anionic surfactants based on fluorocarbon sulfonicacids function at increasingly lower concentrations as the molecularweight of the fluorocarbon chain in the surfactant increases.

The invention described is particularly advantageous for preparingfluorocarbons containing two or more sulfonic acid derivatives. Unlikethe electrochemical cell which gives very poor results when fluorinatingmolecules containing more than one sulfonic acid derivative, materialssuch as these can be prepared in good to moderate yields using theliquid phase fluorination reactor.

This invention also relates to a method of preparing chlorofluorocarbonsby the reaction of chlorinated organics with fluorine gas. The reactiontakes place at temperatures low enough to replace essentially all of thehydrogen atoms with fluorine while retaining all of the chlorine atomspresent in the molecule. For example, telomers of polyvinyl chloride(PVC) can be fluorinated to give telomers of chlorotrifluoroethylenewhich contain chlorine on every other carbon. The regular structureresults because vinyl chloride reacts strictly in a head-to-tailfashion. In contrast, telomers of chlorotrifluoroethylene prepared bypolymerizing chlorotrifluoroethylene have a random structure and, as aresult, are considerably less stable in air ard in the presence of metalsurfaces. The telomers prepared by fluorination of polyvinyl chlorideare presently being contemplated as non-flammable hydraulic fluids.

Similarly, telomers of vinylidene chloride can be fluorinated to yieldchlorofluorocarbons having a regular structure as shown by Equation (8).These materials are also reasonably stable and do not contain chlorineon adjacent carbon atoms. ##STR4##

The invention is further illustrated by the following non-limitingexamples:

EXAMPLE 1

A 10 liter stirred tank reactor was loaded with 5.0 liters1,1,2-trichlorotrifluoroethane. Octanoyl octanoate (877 g) was placed inan erlenmeyer flask and diluted to about 1900 ml with1,1,2-trichlorotrifluoroethane. The nitrogen flow was set at 3400 cc/minand the fluorine flow was set at 800 cc/min. After three minutes, theoctanoyl octanoate solution was added at a rate of 13.7 grams octanoyloctonate per hour or 0.5 ml per minute. The reactor temperature wasmaintained at 0° C. and the condenser temperature at -35° C. After allthe octanoyl octanoate was added (64 hours), the nitrogen flow wasreduced to 1500 cc/min and the fluorine was reduced to 300 cc/min. For30 minutes these flows were maintained while 2 grams of benzenedissolved in 1,1,2-trichlorotrifluoroethane was added at a rate of 4grams per hour of benzene. After 30 minutes of benzene addition, thebenzene flow was stopped. Fifteen minutes after the benzene flow wasstopped, the fluorine was turned off.

After purging with nitrogen, 300 grams technical grade methanol wasadded to the reactor. Approximately seven liters of material was dumpedfrom the reactor which was distilled to yield 2430 grams that boiled at155° C. Analysis of the product showed that much better than 99% of thisfraction was C₇ F₁₅ COOCH₃ (83% yield). The major by-product of thereaction was a dimer of perfluorooctanoic acid (490 g).

EXAMPLE 2

A 10 liter stirred tank reactor was loaded with 5.5 liters1,1,2-trichlorotrifluoroethane. n-Decyl trifluoroacetate (489 g) wasdiluted with 1,1,2-trichlorotrifluoroethane to give a volume of 1600 ml.

The nitrogen flow was set at 2000 cc/min and the fluorine was set at 470cc/min, the reactor was held at -5° C. After four minutes the decyltrifluoroacetate solution was added at 38 ml per hour. Once all thedecyl trifluoroacetate was delivered into the reactor, the fluorine flowwas maintained for an additional 15 minutes to ensure perfluorination.After purging fifteen minutes with nitrogen, 200 grams of technicalgrade methanol was added to the reactor. The products were thendistilled to give 903 grams of C₉ F₁₉ COOCH₃ (88.8% Yield) thatcontained about 0.5% of a material with one or more hydrogens in thefluorinated chain.

EXAMPLE 3

A 10 liter stirred tank reactor was loaded with 5.0 liters1,1,2-trichlorotrifluoroethane. 260 grams of decanoyl chloride wasdiluted with 1,1,2-trichlorotrifluoroethane to give 600 ml of solution.The fluorine was set at 600 cc/min with a nitrogen flow of 2400 cc/min.The reactor temperature was held at 0° C. After five minutes thedecanoyl chloride flow was set at 30 ml/hr. When all of the decanoylchloride was added (20 hours), the fluorine flow was reduced to 300cc/min and the nitrogen to 1200 cc/min and held under these conditionsfor 30 minutes. The fluorine was then turned off and the reactor waspurged with nitrogen for 30 minutes after which time 120 grams ofmethanol was added to the reactor. After distillation 310 grams of C₉F₁₉ COOCH₃ was recovered (43% yield) with the major by-products being C₉F₁₈ ClCOOCH₃, C₉ F₁₇ Cl₂ COOCH₃, and C₉ F₂₀.

EXAMPLE 4

A 10 liter stirred tank reactor was loaded with 5.7 liters1,1,2-trichlorotrifluoroethane. 350 grams of 1,5-pentanediol diacetatewas diluted with 1,1,2-trichlorotrifluoroethane to 700 ml. The nitrogenflow was set at 2000 cc/min and the fluorine flow was set at 570 cc/min.After three minutes the flow of 1,5-pentanediol diacetate was set at 30ml/hr. The reactor temperature was held at -1° C. during the reaction.After all of the pentanediol diacetate had been added (24 hours), thenitrogen flow was set at 1200 cc/min with a fluorine flow of 300 cc/min.Four grams of benzene was placed in 1,1,2-trichlorotrifluoroethane togive 30 ml and this was then pumped into the reactor at a rate of 30ml/hr for 45 minutes. The benzene flow was then stopped and the fluorineflow was terminated 15 minutes later. After purging with nitrogen, 300grams of methanol was added to the reactor. After distillation, 457 g(91.5% yield) of the dimethyl ester of2,2,3,3,4,4-hexafluoropentane-1,5-dioic acid was obtained (b.p. 66°-70°C. at 14 torr). The dimethyl ester can be reduced with lithium aluminumhydride to give a hydroxy-terminated compound with a melt point of 75°C. ##STR5##

EXAMPLE 5

A 10 liter stirred tank reactor was loaded with 5.0 liter1,1,2-trichlorotrifluoroethane. 322 grams of hexanediol diacetate wasplaced in 1,1,2-trichlorotrifluoroethane to give a volume of 640 ml. Thenitrogen flow was set at 1.8 liters per minute while the fluorine flowas set at 590 cc/min. After three minutes, the flow of hexanedioldiacetate was set at 28 ml/hr. The reactor temperature was held at 0° C.during the reaction. Once all of the hexanediol diacetate had been added(23 hours), the nitrogen flow was reduced to 1200 cc/min and thefluorine flow was reduced to 300 cc/min. Four grams of benzene wasdiluted to 30 ml with 1,1,2-trichlorotrifluoroethane and added at a rateof 30 ml/hr for 30 minutes. Ten minutes after the benzene flow wasstopped, the fluorine was turned off and the reactor purged withnitrogen. 300 grams of technical grade methanol was then added to thereactor to make the dimethyl ester of2,2,3,3,4,4,5,5-octafluorohexane-1,6-dioic acid. The product was thendistilled to give 474 grams of a fraction that had a boiling point of108°-110° C. at 30 torr (93.5% yield). The product can be reduced withlithium aluminum hydride to give a hydroxy-terminated derivative with amelt point of 65°-66° C. ##STR6##

EXAMPLE 6

5.0 liters 1,1,2-trichlorotrifluoroethane were placed in a 10 literstirred tank reactor. 291 grams of decanediol diacetate was diluted to660 ml with 1,1,2-trichlorotrifluoroethane and placed in an erlenmeyerflask. The reactor temperature was held at +10° C. during the reactionwhile the nitrogen flow was set a 2 liters/minute and the fluorine flowset at 630 cc/min. After 3 minutes the decanediol diacetate solution wasadded at a rate of 29 ml/hr. Upon completion of the addition (23 hours),the fluorine flow was reduced to 300 cc/min and the nitrogen flowreduced to 1200 cc/min. A solution of 4 grams benzene in 30 ml1,1,2-trichlorotrifluoroethane was then added at a rate of 30 ml/hr for30 minutes. The fluorine flow was allowed to continue for an additional15 minutes then stopped. After purging with nitrogen, 250 grams ofmethanol was added to the reactor to convert the hydrolytically unstableperfluoroester to the relatively stable methyl esters. 402 grams ofmaterial (68.8% yield) was obtained having a boiling point of 102°-113°C. at 0.04 torr. The major impurity was about 150 grams left in thedistillation flask that absorbed strongly in the infrared spectrum inthe CF and carbonyl regions. ##STR7##

EXAMPLE 7

5.0 liters 1,1,2-trichlorotrifluoroethane were placed in a 10 literstirred tank reactor. 307 grams dimethyl phthalate was diluted to 650 mland placed in an erlenmeyer flask. The reactor temperature was held at0° C. during the reaction. The nitrogen flow was set at 1800 cc/min andthe fluorine flow set at 460 cc/min. After 3 minutes the dimethylphthalate solution was added at a rate of 31 ml/hour. Once all thedimethyl phthalate solution was added (21 hours), the nitrogen flow wasreduced to 1200 cc/min and the fluorine flow was reduced to 300 cc/min.Four grams of benzene diluted to 30 ml in 1,1,2-trichlorotrifluoroethanewas then added to the reactor over a one hour period. The fluorine flowwas continued for an additional 15 minutes. After the reactor was purgedwith nitrogen 280 g methanol was added to the reactor. The products werethen distilled at 52 torr to give 171 g of a fraction that boiled below120° C. and 362 g of a fraction that boiled at 120°-128° C. The firstfraction was about 90% pure C₆ F₁₁ COOCH₃ (31.8% yield) with the diacidas the major impurity. The second fraction was shown by gaschromatography to be about 98% pure C₆ F₁₀ (COOCH₃)₂ (60.2% yield) withan equal mixture there of the cis and trans isomers.

EXAMPLE 8

In order to make perfluoro-2-octanone from an ester of 2-octanol, atrimethyl acetate ester of 2-octanol was used because the resultingperfluoroester is fairly resistant to hydrolysis. 5.0 liters1,1,2-trichlorotrifluoroethane were placed in a 10 liter stirred tankreactor. 126.5 grams of the trimethyl acetate ester of 2-octanol wasdiluted to 700 ml in 1,1,2-trichlorotrifluoroethane and placed in anerlenmeyer flask. The reactor temperature was held at -8° C. while thefluorine flow and nitrogen lows were set at 400 and 1500 cc/min,respectively. After three minutes the ester of 2-octanol was added at arate of 39 ml/hr. Upon completing the addition, the fluorine flow andother conditions were maintained for ten additional minutes after whichtime the fluorine flow was stopped and the reactor warmed. The productwas transferred from the reactor in air with no attempt to do anythingextraordinary to prevent hydrolysis. The solvent was removed from thesample by distillation and the bottoms were then transferred to a oneliter nickel reactor where 10 cc/min of F₂ and 40 cc/min of nitrogenwere bubbled through the liquid which was held at 110° C. for four hoursto remove any residual hydrogen left in the sample. After purging withnitrogen this sample was then distilled at atmospheric pressure to give350 grams of a material that boiled at 181°-182° C. (86.8% yield). Thefluorinated product (265 g) was hydrolyzed at elevated temperatures with126 g 1-octanol mixed with 17 g sodium fluoride to giveperfluoro-2-octanone which could be easily separated from the 1-octanolby distillation. The product distilled from the flask as formed (b.p.100°-150° C.). Redistillation of the crude product at 105° C. gave 155 g(96% yield) of perfluoro-2-octanone.

EXAMPLE 9

A 10 liter stirred tank reactor was loaded with 5.4 liters of1,1,2-trichlorotrifluoroethane and 1415 g of finely ground sodiumfluoride powder. The reactor was positioned in a constant temperaturebath which maintained a reactor temperature of -7° C. A condenser, whichwas placed downstream from the reactor, was used to condense and returnto the reactor any liquid vapor which may be in the gas exit line. Thecondenser was maintained at -35° C. A mixture consisting of 328 g of apoly(ethylene glycol)diacetate having an average molecular weight of600, 320 g of 1,1,2-trichlorotrifluoroethane and 113 g of chloroform(used to solubilize the polyether in the 1,1,2-trichlorotrifluoroethane)was slowly metered into the fluorination reactor over a 26 hour period.Fluorine gas, diluted with nitrogen to give a concentration of 20%, wasbubbled through the vigorously stirred fluorination liquid at a rate 10to 15% higher than that required to theoretically replace all of thehydrogen on the hydrocarbon being pumped into the reactor. Following thereaction, the reactor was purged with several volumes of nitrogen toremove the unreacted fluorine gas. Next, 154 g methanol was pumped intothe reactor. The reactor warmed slightly as the perfluorodiester reactedwith the methanol to give the hydrolytically more stable dimethyl ester.The product was filtered to remove the sodium fluoride and sodiumbifluoride solids. The product (mw 1500), which was obtained in about80% yield was separated from the 1,1,2-trichlorotrifluoroethane andmethanol by distillation.

¹⁹ F NMR of the product in chlorotrifluoromethane gave a small-tripletat -77.7 ppm (vs. CFFCl₃) and a large singlet at -88.7 ppm correspondingto the terminal and interior difluoroethylene of perfluoropoly(ethyleneglycol), respectively. ##STR8## No definitive peak corresponding to amonofunctional or nonfunctional compound could be seen in the ¹⁹ F NMR.

EXAMPLE 10

A 252 g sample of poly(ethylene glycol) having an average molecularweight of 1000 was mixed with 400 g of 1,1,2-trichlorotrifluoroethaneand 188 g of trifluoroacetic acid to give a homogeneous solution whichwas slowly pumped into a 10 liter fluorination reactor containing 5.7liters of 1,1,2-trichlorotrifluoroethane and 1150 g of sodium fluoridepowder. The reactor was maintained at 10° C. as 20% fluorine wasdelivered at a rate sufficient to react with all of the organic beingfed into the reactor. The reaction was complete in approximately 26hours. Filtration of the product, followed by removal of thefluorination liquid gave 535 g of perfluoropoly(ethylene oxide).Treatment of the fluid for several hours at 250° C. with 30% fluorineconverted the reactive terminal groups to perfluoroalkyl groups. Thefluid was distilled into fractions having the following physicalproperties:

    __________________________________________________________________________              Fraction                                                            Property  1    2    3     4     5                                             __________________________________________________________________________    Boiling point range                                                                     <200(100)                                                                          >200(100)                                                                          >245(10)                                                                            >288(0.05)                                                                          >343(0.05)                                    °C. (mm Hg)                                                                           <245(10)                                                                           <288(0.05)                                                                          <343(0.05)                                          % of total                                                                              13   40   36    7     4                                             Kinematic                                                                     Viscosity (cst.)                                                              20° C.                                                                           3.32 13.2 33.9  127.00                                                                              447.00                                        40° C.                                                                           2.07 7.21 16.1  51.9  173.00                                        60° C.                                                                           1.43 4.25 9.05  26.7  82.9                                          80° C.                                                                           1.05 2.80 5.73  15.5  44.9                                          95° C.                                                                           0.85 2.09 4.19  11.1  --                                            149° C.                                                                          0.46 1.07 1.93  4.27  11.4                                          ASTM slope                                                                              0.934                                                                              0.725                                                                              0.681 0.538 0.488                                         Density (20° C., g/ml)                                                           1.7484                                                                             1.7650                                                                             1.7883                                                                              1.8133                                                                              1.8234                                        __________________________________________________________________________

¹⁹ F NMR of fraction #4 in CFCl₃ gave the following results: (δ ppm vsCFCl₃) -56.0 (t, 9.6 Hz, a); -89.0 (s,c) and -91.0 (q, 9.6 Hz, b)##STR9##

Anal. Calcd. for C₂ F₄ O: C, 20.69; F, 65.17. Found: C, 20.77; F, 65.29

EXAMPLE 11

In an experiment similar to Example 10, 252 g of a poly(ethylene glycol)having an average molecular weight of 1540 was diluted with 500 ml1,1,2,-trichlorotrifluoroethane, 87 g trifluoroacetic anhydride and 74 gof trifluoroacetic acid. The homogeneous solution was pumped over a 28hour period into a 10° C. fluorination reactor containing 5.7 liters of1,1,2-trichlorotrifluoroethane and 1150 g of sodium fluoride powder.Following filtration and distillation of the product, 398 g of aperfluorinated fluid was recovered (60% yield) along with a small amountof elastomeric solids. The fluid had a composition identical to thefluid described in the previous example and a molecular weight of 2,500amu.

EXAMPLE 12

A perfluoropolyether elastomer was prepared by dissolving 146 g of an18,500 a.m.u poly(ethylene glycol) in 354 g of chloroform containing 564g of 1,1,2-trichlorotrifluoroethane. The viscous solution was slowlypumped into a 10° C. reactor containing 5 liters of1,1,2-trichlorotrifluoroethane and 800 g of sodium fluoride. Twentypercent fluorine, diluted with nitrogen, was metered into the reactorthroughout the reaction which lasted approximately 28 hours. Followingthe reaction, the product was filtered to give a clear filtrate whichcontained 14.5 g of a polymeric fluid (3.8%). The insoluble portion ofthe product consisted of sodium fluoride, sodium bifluoride andperfluoropoly(ethylene oxide) solids (81% yield) having the followingstructure:

    CF.sub.3 O(CF.sub.2 CF.sub.2 O).sub.n CF.sub.3

The solids were pressed into thin elastomeric sheets using alaboratory-size mill. The polymer remained elastic over a temperaturerange of -80° C. to +360° C.

EXAMPLE 13

Five hundred grams of poly(tetramethylene ether) glycol having anaverage molecular weight of 1000 were treated with a 50% molar excess ofacetyl chloride to convert the hydroxyl end groups of the polymer toacetate groups. The acetylated polymer (288 g) was mixed with 500 ml1,1,2-trichlorotrifluoroethane and was slowly pumped into a 10 literreactor containing 5 liters of 1,1,2-trichlorotrifluoroethane and 1400 gof sodium fluoride powder. The reactor temperature was maintained at 5°C. while 20% fluorine was metered into the reactor at a rate sufficientto react with the organic being delivered. Following the reaction, theproduct was filtered to remove the sodium fluoride and the filtrate wasconcentrated to give 700 g of a fluorinated oil (81% yield) which wastreated for 12 hours at 2700C with 30% fluorine to remove any remaininghydrogens and to convert the terminal esters to nonreactiveperfluoroalkyl groups. Approximately 40% of the oil distilled between200° and 300° C. at 0.05 mm Hg. The average molecular weight by ¹⁹ F NMRend group analysis was 3054. The fluid had a pour point of -50° C.

    ______________________________________                                        Viscosity of                                                                  Perfluoropoly(tetramethylene ether) glycol                                    Temperature    Viscosity                                                                              Slope                                                 °C.     (cst.)   ASTM #D341                                            ______________________________________                                        20             164.9                                                          80             14.61    -0.654                                                150            3.29                                                           ______________________________________                                    

    ______________________________________                                        .sup.19 F NMR data for                                                        Perfluoropoly(tetramethylene ether) glycol                                                 δ (Multiplicity)                                                                     J(F-F)  Rel. Inten.                                 Structure    ppm vs CFCl.sub.3                                                                          Hz      %                                           ______________________________________                                        CF.sub.3 O   -55.7 (t)    18.3    0.2                                         CF.sub.3 CF.sub.2 CF.sub.2 O                                                               -81.9 (t)     7.3    4.9                                         OCF.sub.2 CF.sub.2 CF.sub.2 CF.sub.2 O                                                     -83.3 (s)            42.6                                        CF.sub.3 CF.sub.2 CF.sub.2 O                                                                -84.3 (m)           3.3                                         CF.sub.3 CF.sub.2 O                                                                        -87.3 (s)            0.8                                         CF.sub.3 CF.sub.2 O                                                                        -88.5 (p)            0.5                                         OCF.sub.2 CF.sub.2 CF.sub.2 CF.sub.2 O                                                     -125.7 (s)           42.6                                        CF.sub.3 CF.sub.2 CF.sub.2 O                                                               -130.0 (s)           3.3                                         ______________________________________                                         Anal. Calcd. for CF.sub.3 CF.sub.2 CF.sub.2 O(CF.sub.2 CF.sub.2 CF.sub.2      CF.sub.2 O).sub.12.5 --CF.sub.2 CF.sub.2 CF.sub.3 : C, 22.00; F, 70.92.       Found: C, 21.87; F, 70.02                                                

EXAMPLE 14

Using the procedures outlined in Example 9, a solution consisting of 280g of poly(tetramethylene ether)glycol (terminal groups treated withacetyl chloride to give a diester) having an average molecular weight of2000 and 550 ml of 1,1,2-trichlorotrifluoroethane was slowly metered,over a 32 hour period, into a 5° C. fluorination reactor containing 5liters of 1,1,2-trichlorotrifluoroethane and 1400 g of sodium fluoridepowder. Upon completing the reaction, the reactor was purged withseveral volumes of nitrogen to remove the unreacted fluorine gas.Methanol (150 g) was added to the reactor. The reactor contents werefiltered to give a clear filtrate which upon removal of the1,1,2-trichlorotrifluoroethane and unreacted methanol via a distillationgave a nearly quantitative yield of perfluoropoly(tetramethyleneether)dimethyl ester (mw 4250).

EXAMPLE 15

Into a 500 cc stainless steel pressure vessel were placed 250 g1,2-epoxybutane and 1 g ferric chloride catalyst. The reactor was rockedin an 80° C. oven for approximately 96 hours during which time theepoxide polymerized to give a high molecular weight semisolid. Thepolymer was dissolved in 1 liter of 1,1,2-trichlorotrifluoroethane andpumped into a fluorination reactor using the procedures outlined inExample 9. The reactor, which contained 5 liters of1,1,2-trichlorotrifluoroethane and 1250 g sodium fluoride powder, washeld at 0° C. with a constant temperature bath. Following the 22 hourreaction, 750 g of fluid was recovered which was further fluorinated at300° C. with 30% fluorine for an additional 24 hours to give 660 g offluid (88% yield). Approximately 220 g of fluid distilled between 200°and 300° C. at reduced pressure (0.05 mm Hg) with approximately equalamounts boiling below and above that range. The average molecular weightof the mid-fraction was 1850 (by ¹⁹ F NMR end group analysis). The fluidhad a pour point of -9° C.

    ______________________________________                                        Viscosity Of Perfluoropoly(1,2-epoxybutane)                                   bp > 200° C. and <300° C @ 0.05 mm Hg                           Temp         Viscosity                                                                              Slope                                                   (°C.) (cst.)   ASTM #D341                                              ______________________________________                                        20           5688                                                             80           72.9     -0.725                                                  150          6.52                                                             ______________________________________                                    

    ______________________________________                                        .sup.19 F NMR of Perfluoropoly(1,2-epoxybutane)                                              δ (Multiplicity)                                                                     Rel. Inten.                                       Structure      ppm vs CFCl.sub.3                                                                          %                                                 ______________________________________                                        CF.sub.2 CF(C.sub.2 F.sub.5)O                                                                -77.3, -80.0, 82.2                                                                         23.3                                              CF.sub.2 CF(CF.sub.2 CF.sub.3)O                                                              -81.0 (s)    35.3                                              CF.sub.3 CF.sub.2 CF.sub.2 O                                                                 -82.0 (m)    4.2                                               CF.sub.3 CF.sub.2 CF.sub.2 O                                                                 -84.7 (m)    2.8                                               CF.sub.2 CF(CF.sub.2 CF.sub.3)O                                                              -120 to 127  23.3                                              CF.sub.3 CF.sub.2 CF.sub.2 O                                                                 -130.3       2.8                                               CF.sub.2 CF(C.sub.2 F.sub.5)O                                                                -141.2 (m)   7.8                                               ______________________________________                                    

EXAMPLE 16

A potentially useful nonflammable hydraulic fluid was prepared byplacing in a 3 liter, 3 neck flask equipped with a mechanical stirrer,80 g 2-chloroethanol (1.0 mol) and 1 ml boron trifluoride-etherate. Tothis solution, 462 g epichlorohydrin (5.0 mol) was added over a one hourperiod while the reaction temperature was maintained below 50° C.throughout the addition. The mixture was stirred for an additional 12hours at ambient temperature resulting in the formation of a veryviscous fluid. The product (403 g) was dissolved in 164 g chloroformcontaining 405 g 1,1,2-trichlorotrifluoroethane. This solution wasmetered into an 18° C. reactor which contained 5 liters of1,1,2-trichlorotrifluoroethane. Fluorine gas (20%) was introduced at arate which was approximately 5% greater than the theoretical amountrequired to react with all of the hydrogens on the material entering thereactor. Upon completion of the reaction which lasted approximately 20hours, the reactor was purged with nitrogen to remove the unreactedfluorine gas.

Distillation of the product to remove the fluorination liquid gave 620 gof a perfluorinated fluid having substantially the following structure:

    ClCF.sub.2 CF.sub.2 O(CF.sub.2 CF(CF.sub.2 Cl)O).sub.n CF.sub.2 CF.sub.2 Cl

M.W. 848; Density (37.8° C.): 1.7973 g/ml Bulk modulus (37.8° C. and3,000 PSIG): 129,700 PSIG Elemental Analysis: Calculated for an averagestructure C₂.11 F₄.42 Cl₀.8 O(C₃ F₅ ClO)₃.05 C₂.11 F₄.42 Cl₀.8 C, 18.92;F, 53.98; Cl, 1944 Found: C, 18.86; F, 51.15; Cl, 18.26%

A further treatment of the above product with 30% fluorine at 225° C.converted the carbonyl to a difluoromethylise group (618 g). Followingtreatment of the product at elevated temperatures with fluorine theproduct was distilled. The portion boiling between 50° C. and 150° C. at2 mm Hg was collected (80% of the sample) and was shown to be a verypromising hydraulic fluid candidate. The bulk modulus of the materialwas measured using an isothermal secant method. The following resultswere obtained.

    ______________________________________                                        Perfluoropolyepichlorohydrin Type I Bulk Modulus                              M.sub.B @ PSI                                                                 °F. @ PSI                                                                        1000    2000       3000  4000                                       ______________________________________                                        100° F.                                                                          129,500 136,700    138,600                                                                             145,100                                    150° F.                                                                          180,700 104,200    109,700                                                                             115,400                                    ______________________________________                                    

    ______________________________________                                        Viscosity of Perfluoropolyepichlorohydrin Type I                              Hydraulic Fluid (monochloro end group)                                        Temp °F.                                                                            Viscosity (cst.)                                                 ______________________________________                                        -65          1198                                                             100          3.5                                                              176          1.42                                                             ______________________________________                                    

EXAMPLE 17

A high molecular weight perfluoropolyepichlorohydrin fluid, havingproperties similar to those required for a vacuum pump fluid, wasprepared by reacting 50 g 2-chloroethanol (0.63 mol) with 462 gepichlorohydrin (5.0 mol) using a catalytic amount of SnCl₄. The product(402 g), diluted with 275 g chloroform and 175 g1,1,2-trichlorotrifluoroethane, was metered into a fluorination reactorover a 20 hour period. The reactor, a 10 liter stirred tank, contained5.7 liters 1,1,2-trichlorotrifluoroethane. During the course of thereaction the temperature was maintained near 20° C. while 20% fluorinewas delivered to the reactor at a rate sufficient to react with all ofthe hydrogens on the product being pumped in. The fluorinated product(573 g, 89.8% yield) was separated from the solvent via an atmosphericdistillation. The product was treated at 200° C. for 12 hours to removeany residual hydrogen and to convert any carbonyl groups present todifluoromethylenes. The portion of the product, approximately 25%,having a boiling point between 200° and 300° C. at 0.05 mm Hg wascollected. The average molecular weight by ¹⁹ F NMR end group analysiswas approximately 3000. The fluid had a pour point of -22° C.

    ______________________________________                                        Viscosity Of Perfluoropolyepichlorohydrin                                     Vacuum Pump Fluid                                                             Temp.        Viscosity                                                                              Slope                                                   (°C.) (cst.)   ASTM #D341)                                             ______________________________________                                        20           953.7                                                            80           26.54    0.763                                                   150          4.11                                                             ______________________________________                                    

    ______________________________________                                        .sup.19 F NMR of fraction boiling between 200 and 300° C. at           0.05 mm Hg (δ ppm vs CFCl.sub.3):                                       -53.3(f), -67.2(e), -68.6(i), -74.2(a), -77.0 &                               -81.0(c), -79.0(g), -87.3(b), -123.7(h), and                                  -139.3(d).                                                                    CF.sub.2 ClCF.sub.2 O CF.sub.2 CF(CF.sub.2 Cl)O!.sub.n --CF.sub.3 or          --CF.sub.2 CF.sub.2 CF.sub.2 Cl                                               a      b     c     d   e     f     g   h   i                                  or CF.sub.2 CF.sub.2 Cl                                                       ______________________________________                                    

EXAMPLE 18

Into a 10 liter, 3 neck flask equipped with a mechanical stirrer werecharged 860 g 1,3-dichloro-2-propanol (617 mol) and 4 ml borontrifluorideetherate. To this solution was added 1.8 Kg epichlorohydrin(20 mol) over a 2 hour period as the temperature was maintained below50° C. throughout the addition with a water bath. The mixture wasstirred for an additional 12 hours at ambient temperature resulting in avery viscous oil.

A portion of the above epichlorohydrin telomer (1,660 g) was dissolvedin 164 g chloroform containing 405 g 1,1,2-trichlrotrifluoroethane. Thesolution was metered into a 10 liter stirred fluorination reactorcontaining 5.0 liters of 1,1,2-trichlorotrifluoroethane. The reactor washeld at 20° C. throughout the addition as fluorine gas (20%), dilutedwith nitrogen, was delivered at a rate slightly above that required totheoretically react with all of the organic feed. The reaction wascomplete in 36 hours. The crude product was recovered from the solventby an atmospheric distillation. Treatment of the product with 30%fluorine at 200° C. for 12 hours resulted in 4100 g of an inert fluid ofwhich approximately 80% boiled between 50° and 150° C. at 2 mm Hg.

The fluid was shown by ¹⁹ F NMR end group analysis to have an averagemolecular weight of 850.

Density (37.8° C.): 1.7966 g/ml Bulk modulus (37.8° C. and 3,000 PSIG):135,400 PSIG Elemental analysis calculated for an average structure of:C₂.31 F₄.46 Cl₁.15 O(C₃ F₅ ClO)₂.89 C₂.31 F₄.46 Cl₁.15 C, 18.77; F,52.26; Cl, 21.65 Found: C, 18.85; F, 53.13; Cl, 21.51%

    ______________________________________                                        Viscosity of Perfluoropolyepichlorohydrin Type II                             Hydraulic Fluid (Dichloro end group)                                          Temp (°F.)                                                                           Viscosity (cst.)                                                ______________________________________                                        -65           1130                                                            100           3.35                                                            ______________________________________                                    

¹⁹ F NMR (δ ppm vs CFCl₃) -53.3(f), -65.6(a), -67.2(e), -68.6(k),-74.3(h), -77.0(c), -79.0(i), -87.3(g), -123.7(j), -135.2(b) and-139.3(d). ##STR10##

EXAMPLE 19

Trichloropentaerythritol was prepared by bubbling hydrogen chloride gasinto a mixture of 600 g acetic acid and 100 g of water at 0° C. until176 g had been absorbed (4.9 mol). This mixture was charged into anautoclave along with 200 g pentaerythritol (1.5 mol). The autoclave wassealed and heated to 160° C. for 8 hours. Upon completion of thereaction, the autoclave was cooled to room temperature and the reactionmixture was diluted with water. Trichloropentaerythritol acetate wasisolated by extraction with methylene chloride. The solvent was removedand the residual oil was refluxed overnight with 500 ml of methanol and50 ml of concentrated hyurochloric acid. Trichloropentaerythritolcrystallized from the solution as the methanol md methyl acetate wasslowly removed by distillation. The crude product (275 g) has a meltingpoint of 60° C.

A 3 liter flask was charged with 267 g of trichloropentaerythritol and 1ml of boron trifluorideetherate. To this was added 347 g ofepichlorohydrin (3.75 mol) dropwise over a one hour period while thereaction temperature was maintained below 50° C. throughout theaddition. The mixture was stirred for an additional 12 hours at ambienttemperature resulting in a viscous oil.

The product (612 g), diluted with 210 g of chloroform and 217 g of1,1,2-trichlorotrifluoroethane, was fluorinated in the usual manner in a20° C. reactor containing 3.7 liters of 1,1,2-trichlorotrifluoroethane.The reaction was complete in approximately 30 hours. The fluid (1,460 g)was stabilized by treatment with 30% fluorine for 12 hours at 210° C.The fluid was distilled and the portion boiling between 170° C. and 230°C. at 50 mm Hg had a viscosity suitable for hydraulic fluidapplications. Average molecular weight of the product was 855.

    ______________________________________                                        Viscosity of Perfluoroepichlorohydrin Type III                                Hydraulic Fluid (Trichloro end groups)                                        Temp (°F.)                                                                           Viscosity (cst.)                                                ______________________________________                                        -65           1150                                                            104           3.06                                                            176           1.46                                                            ______________________________________                                    

¹⁹ F NMR (δ ppm vs CFCl₃) -48.7(a), -53.3(f), -67.2(e), -68.5(k),-74.3(h), -77.0(c), -78.8(i), -80.6(b), -87.3(g), -123.8(j) and -140(d).##STR11##

EXAMPLE 20

Butoxyethoxyethanol (300 g, 1.85 mol) was treated with 200 g acetylchloride (2.54 mol) to give an ester which was separated from theproduct mixture by distillation. A portion of the product (250 g) wasdiluted to a volume of 610 ml with 1,1,2-trichlorotrifluoroethane, thenpumped into a -10° C. reactor over a 23 hour period. Fluorine gas,diluted with nitrogen, was delivered to the reactor which contained 5liters of 1,1,2-trichlorotrifluoroethane and 1200 g sodium fluoridepowder. Upon completion of the reaction, 160 g methanol was pumped intothe reactor to give the methyl ester which is considerably morehydrolytically stable than the perfluoro ester made in the reaction. Theproduct (M.W. 460) was obtained in 96% yield. ##STR12##

EXAMPLE 21

A diacetate ester of tetraethylene glycol was prepared by slowly adding600 g acetyl chloride to 500 g tetraethylene glycol in a stirred 2-literflask. Upon addition of the acetyl chloride, the reaction mixture washeated to 50° C. and held at that temperature for 24 hours. Dry nitrogenwas bubbled through the flask for 24 hours to remove the hydrogenchloride, then the product was distilled to give a quantitative yield ofthe desired product.

The product from the above reaction (247.7 g) was fluorinated in areactor containing 5 liters 1,1,2-trichlorotrifluoroethane and 120 gsodium fluoride. The reactor was held at -10° C. for approximately 20hours as the organic was slowly pumped into the reactor. Upon completionof the addition, the unreacted fluorine was swept from the reactor withnitrogen gas and 200 g of methanol was added to give the followingproduct in 93% yield (M.W. 466).

¹⁹ F NMR (δ ppm vs CFCl₃): -77.6(a) and -88.4(b). ##STR13## The aboveproduct was reduced with lithium aluminum hydride in tetrahydrofuran togive the expected methylol derivative in approximately 90% yield.

EXAMPLE 22

A diacetate ester of triethylene glycol was prepared by slowly adding400 g acetyl chloride (5.1 mol) to 300 g triethylene glycol (2.0 mol) ina stirred 1 liter flask. The reaction mixture was kept below 50° C.throughout the addition. The product was recovered by first bubbling drynitrogen through the solution to remove most of the hydrogen chloridefollowed by a distillation.

The product from the above reaction (250 g) was diluted to 600 ml with1,1,2-trichlorotrifluoroethane then pumped into a -20° C. reactorcontaining 5 liters of 1,1,2-trichlorotrifluoroethane and 1200 g sodiumfluoride powder. Fluorine, diluted with nitrogen, was bubbled throughthe liquid fluorination medium throughout the addition which requiredapproximately 18 hours. After purging the reactor for approximately 30minutes, 240 g methanol was added and the reactor was warmed to roomtemperature. Distillation of the reactor contents gave 355 grams (95%yield) of a product with the following composition.

¹⁹ F NMR (δ ppm vs CFCl₃): -77.6(a) and -88.3(b) ##STR14## The dimethylester was reduced with lithium aluminum anhydride to give the methylolderivative. ##STR15##

EXAMPLE 23

A 200 g sample of polypropylene glycol having an average molecularweight of 425 was diluted to 350 ml with 1,1,2-trichlorotrifluoroethaneand slowly pumped into a 20° C. fluorination reactor over a 22 hourperiod. The reactor contained 4 liters of 1,1,2-trichlorotrifluoroethaneas the fluorination liquid. In a separate vessel, 1000 g sodium fluoridepellets were placed. A teflon-diaphragm air pump was used to circulatethe gases present in the reactor through the sodium fluoride bed andback into the fluorination reactor. Gas velocities in the recirculatingloop of approximately 10 to 20 liters per minute were sufficient tosweep out most of the hydrogen fluoride formed in the reaction so thatreasonable fluorination yields could be achieved. Following thereaction, 307 g of product (M.W. 1200) was isolated by distillation(53.7%).

EXAMPLE 24

In an experiment similar to the one previously described, 202 gpolypropylene glycol (425 MW) was fluorinated in a reactor containing3.7 liters of 1,1,2-trichlorotrifluoroethane. Once again, 1000 g sodiumfluoride pellets were placed in a container which was connected to thefluorination reactor by a circulating gas loop. The reaction temperaturewas increased to 30° C. to see if the hydrogen fluoride could be removedmore efficiently. The product (356 g) was isolated in 62.2% yield.

Unlike the isotactic perfluoropoly(propylene oxide) which can be made bypolymerizing hexafluoropropylene oxide, the perfluorinated fluidsdescribed in this example and the previous one were a tactic polymers ofhexafluoropropylene oxide. The hexafluoropropylene oxide units wereattached in a head to tail, head to head and tail to tail fashion.Because of the random structure of these fluids, slightly improved lowtemperature properties were typically obtained.

EXAMPLE 25

To a stirred solution consisting of 194 g tetraethylene glycol (1.0 mol)and 4.0 g of 50% sodium hydroxide was added 111 g acrylonitrile (2.1mol).

The reaction mixture was stirred for three hours at room temperature.500 ml ethanol was added to the mixture followed by the slow addition of214 ml of concentrated sulfuric acid (4.0 mol). Upon completion of theaddition, the mixture was refluxed for seven hours, cooled, thenfiltered to remove the precipitated solids (NH₄ HSO₄). The solids weredashed with ethanol and the organic phase was combined with the ethanolrinse solution to give a mixture which upon distillation yielded aproduct with the following structure (90% yield). ##STR16##

Fluorination of 305 grams of the polyether in a 10° C. reactorcontaining 5 liters of 1,1,2-trichlorotrifluoroethane and 1200 g sodiumfluoride, followed by treatment with methanol gave 568 g of fluid (M.W.798) having the following structure (92% yield). ##STR17##

EXAMPLE 26

In an experiment similar to the previous one, 194 g tetraethylene glycol(1.0 mol) was reacted with 140 g metacrylonitrile (2.1 mol) in thepresence of 4.0 g 50% sodium hydroxide. Treatment of the resultingdinitrile with ethanol and concentrated sulfuric acid yielded thediethyl ester.

Fluorination of the diester (300 g) using a fluorination proceduresimilar to that described in the previous example gave 630 g of theproduct shown below (91% yield). ##STR18##

EXAMPLE 27

Using the procedure outlined in Example 25, dipropylene glycol methylether was treated with acetonitrile to give a material which upontreatment with ethanol in the presence of sulfuric acid gave of materialhaving the following structure: ##STR19##

Fluorination of 213 g of the material in a -10° C. reactor containing5.3 liters of 1,1,2-trichlorotrifluoroethane and 1050 g of sodiumfluoride powder gave a perfluorinated ester which upon treatment withmethanol gave 258 g of a functional fluid corresponding to the followingstructure. ##STR20##

bp 75° C./15 mm Hg

EXAMPLE 28

Cyclohexene oxide (250 g) was polymerized in 1 liter of n-hexane at -0°C. using a catalytic amount of triethylaluminum. The reaction wascomplete in approximately 1 hour. The polymer was first washed withconcentrated HCl, then water followed by several rinses with methanol.

Fluorination of the polymer (205 g) using the fluorination techniquesoutlined in previous examples gave 413 g of a perfluorinated fluid (71%yield).

EXAMPLE 29

200 g polyoxetane was diluted to a volume of 500 ml and was slowlypumped into a 20° C. fluorination reactor containing 5 liters1,1,2-trichlorotrifluoroethane and 1000 g sodium fluoride powder. Thepolymer was prepared via a ring opening polymerization of oxetane or bydehydration of 1,3-propanediol. The fluorinated product, 335 g, wasrecovered by first removing the sodium fluoride by filtration followedby distillation to remove the fluorination solvent.

¹⁹ F NMR of a sample having a boiling point of 200°-300° C./0.05 mm Hg:##STR21##

EXAMPLE 30

Into a 1 liter stirred flask equipped with a water separator were placed500 g diethylene glycol (4.7 mol), 90 g diethylene glycol methyl ether(10.75 mol), 225 g paraformaldehyde (7.5 mol), 150 ml toluene and 5 gion exchange resin (H⁺ form). The mixture was refluxed for several hoursto remove the water formed during the reaction. The solution was firstfiltered to remove the ion exchange resin, then distilled to 150° C. at0.05 mm/Hg to remove the toluene and other lights. A nearly quantitativeyield of polymer having an average molecular weight of 1500 wasobtained.

320 g of polymer, mixed with 170 g chloroform and 300 g1,1,2-trichlorotrifluoroethane was slowly pumped over a 23 hour periodinto a 15 liter stirred fluorination reactor containing 6 liters of1,1,2-trichlorotrifluoroethane and 1300 g of sodium fluoride powder. 20%fluorine was bubbled through the liquid fluorination medium at a rate15% higher than that required to theoretically replace all of thehydrogen on the hydrocarbon being pumped into the reactor. The reactortemperature was maintained between 0° and +10° C. throughout thereaction. Following the reaction, the reactor contents were filtered andthe liquid fluorination medium (1,1,2-trichlorotrifluoroethane) wasremoved from the filtrate via an atmospheric distillation to 120° C. togive 535 g of crude fluid (66%). Fluorination of the fluid at 260° C.gave a clear, colorless fluid which was shown by elemental analysis and¹⁹ F NMR to have the following structure:

    (CF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 O).sub.n

EXAMPLE 31

400 g butoxyethoxyethanol (2.5 mol), 48 g paraformaldehyde (1.6 mol),300 ml benzene and 5 g ion exchange resin (acid form) were placed in a 1liter stirred flask. A water separator attached to a reflux condenserwas used to collect the water produced as the alcohol and aldehydereacted. After approximately 6 hours, the reaction was complete and thesolution was filtered to remove the resin. Vacuum distillation of thesolution to 120° C. gave 414 g of a product (99% yield) which wasessentially free of benzene and unreacted starting materials.

The hydrocarbon product was fluorinated in a 22 liter stirred tankreactor which contained 6 liters of 1,1,2-trichlorotrifluoroethane and1300 g sodium fluoride powder. A gas dispersion tube in the bottom ofthe reactor provided an inlet for the fluorine and nitrogen gasses. 275grams of the hydrocarbon reactant was diluted with1,1,2-trichlorotrifluoroethane, in a separate vessel, to give a totalvolume of 700 ml. This solution was metered into the fluorinationreactor over a 20 hour period. The reactor temperature was maintained at0° C. with external cooling throughout the reaction while the fluorineflow was set at a level 10% higher than that required to theoreticallyreplace all of the hydrogens on the material entering the reactor. Uponcompletion of the reaction, the fluorine was turned off, the reactor wasremoved from the low temperature bath and purged for 30 min withnitrogen (2 liters/min) to remove the unreacted fluorine.

Filtration of the reaction product followed by distillation to removethe 1,1,2-trichlorotrifluoroethane gave 642 g of a highly fluorinatedfluid (80% yield). Treatment of the fluid at 260° C. with 30% fluorinefor several hours gave a perfluorinated fluid having essentially thefollowing structure:

    CF.sub.3 CF.sub.2 CF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 Cf.sub.2 CF.sub.2 CF.sub.3

The elemental analysis was consistent with the formula:

17F₃₆ O₆.

b.p. 226.5° C.

¹⁹ F NMR (δ ppm vs CFCl₃): -89.0, -90.7: CF₂ CF₂ O; -51.8: CF₂ O; -81.8,-83.7, -126.7: CF₃ CF₂ CF₂ CF₂ O.

EXAMPLE 32

A mixture of 400 g triethylene glycol monoethyl ether (2.2 mol), 48 gparaformaldehyde (1.6 mol), 150 ml toluene and 10 g of an acid ionexchange resin was refluxed for 6 hours in a 1 liter flask equipped witha water separator and reflux condenser. Filtration of the productfollowed by distillation gave a quantitative yield of the desiredproduct.

Fluorination of 201 g of the material in a stirred liquid fluorinationreactor containing 6 liters of 1,1,2-trichlorotrifluoroethane and 1055 gsodium fluoride gave 401 g fluid in an 18 hour reaction at 0° C.Distillation of the crude product mixture gave 355 g of theperfluorinated fluid:

    CF.sub.3 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.3

C₁₇ O₈ F₃₆

b.p. 217° C.

¹⁹ F NMR (δ ppm vs CFCl₃): -51.7: CF₂ O; -87.3, -90.7: CF₃ CF₂ ; -88.7CF₂ CF₂ O.

EXAMPLE 33

Into a 1 liter flask were placed 600 g triethylene glycol butyl ether(2.91 mol), 74 g paraformaldehyde (2.46 mol), 150 ml benzene and 10 g ofan acidic ion exchange resin. The mixture was refluxed for 5 hours aswater was removed as the water/benzene azeotrope. Filtration of theproduct and removal of the benzene by distillation gave a 90% yield ofthe polyether. 259 grams of the product was diluted with 400 ml1,1,2-trichlorotrifluoroethane and was slowly metered into a 10° C.reactor containing 5.7 liters of 1,1,2-trichlorotrifluoroethane and 1200g sodium fluoride powder. A fluorocarbon fluid (660 g, 88.7% yield) wasobtained following filtration and removal of the1,1,2-trichlorotrifluoroethane. Fluorination of the fluid at 220° C.with 30% fluorine for 12 hours followed by distillation gave thefollowing fluid in 60% yield:

    CF.sub.3 CF.sub.2 CF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 CF.sub.2 CF.sub.3

b.p. 262° C.

¹⁹ F NMR (δ ppm vs CFCl₃): -88.7, -90.5: CF₂ CF₂ O; -51.7: CF₂ O; -81.6,-83.4, -126.5: CF₃ CF₂ CF₂ CF₂ O.

EXAMPLE 34

Into a stirred 1 liter flask equipped with a water separator werecharged 350 g tetraethylene glycol butyl ether (1.40 mol), 35 gparaformaldehyde (1.18 mol), 200 ml benzene and 10 g ion exchange resin.The mixture was refluxed until the water production ceased. Filtrationof the product followed by removal of the lights via a vacuumdistillation to 140° C. gave 343 g of a light yellow fluid.

A 306 g sample of the fluid was diluted with 450 ml of1,1,2-trichlorotrifluoroethane and slowly pumped into a -6° C. reactorover a 23 hour period. The reactor contained 1450 g of sodium fluoridepowder to react with the hydrogen fluoride formed during the reactionalong with 6 liters of 1,1,2-trichlorotrifluoroethane. Filtration of theproduct followed by distillation gave 736 g of fluid.

Treatment of the fluid at 250° C. with 30% fluorine gave a clear,odorless fluid which upon distillation gave a 52% yield of a materialhaving the following structure:

    CF.sub.3 CF.sub.2 CF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 OCF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 CF.sub.2 CF.sub.3

b.p. 296.7° C.

¹⁹ F NMR (δ ppm vs CFCl₃): -51.8: CF₂ O; -88.8, -90.6: CF₂ CF₂ O; -81.7,-83.6, -126.7: CF₃ CF₂ CF₂ CF₂ O.

EXAMPLE 35

In a similar experiment, 400 g tetraethylene glycol (2.06 mol), 109 gparaformaldehyde (3.62 mol), 17 g triethylene glycol methyl ether (0.103mol), 150 ml benzene and 5 g ion exchange resin were allowed to react ina 1 liter flask containing a water separator. After 6 hours, thecontents of the flask were filtered and the lights were removed via avacuum filtration. A 265 g sample of the polymer was mixed with 160 gchloroform and 285 g 1,1,2-trichlorotrifluoroethane. The polymericsolution was metered, over a 22 hour period, into a stirred 10 literfluorination reactor which contained 1150 g sodium fluoride powder and4.5 liters of 1,1,2-trichlorotrifluoroethane. The reactor was maintainedat 7° C. while 20% fluorine (diluted with nitrogen) was metered into thereactor at a rate sufficient to react with all of the organic enteringthe reactor. Upon completion of the reaction, the solution was filteredand the liquid fluorination medium was removed via a distillationyielding 422 g (62% yield) of a clear, stable fluid The product wasfractionated into three samples, one which boiled below 200° C. at 0.05mm Hg (40%), a second which boiled between 200° and 300° C. at 0.05 mm(35%) and a third having a boiling point above 300° C. at 0.05 mm Hg(25%). The intermediate fraction had a viscosity of 33.1 cst. at 20°,6.3 cst. at 80° and 2.13 cst. at 150° C. and an average molecular weightof 2560 by ¹⁹ F NMR. The pour point was -79° C. The analysis wasconsistent with the formula:

    (CF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 CF.sub.2 O).sub.n

¹⁹ F NMR (δ ppm vs CFCl₃) -51.8: CF₃ O; -56.0: CF₃ O; -88.8, -90.6: CF₂CF₂ O.

Anal. Calcd. for C₉ F₁₈ O₅ : 20.4, C; 64.5, F. Found. 21.0, C; 65.1, F.

EXAMPLE 36

Dipropylene glycol methyl ether (300 g, 2.04 mol), 60.8 gparaformaldehyde (2.03 mol), 100 ml toluene and 5 g of an acid catalystwere mixed in a stirred 1 liter flask. After refluxing for 12 hours, thesolution was filtered and distilled to give 203 g of a fluid whichboiled at 140° C. at 0.05 mm Hg. The fluid (200 g) was mixed with 300 ml1,1,2-trichlorotrifluoroethane and 950 g sodium fluoride powder. Thereaction was complete in 18 hours after which time the solution wasfiltered and distilled to give 405 g of a clear liquid having thefollowing structure (71% yield):

    CF.sub.3 OC.sub.3 F.sub.6 OC.sub.3 F.sub.6 OCF.sub.2 OC.sub.3 F.sub.6 OC.sub.3 F.sub.6 OCF.sub.3

The fluid contains CF(CF₃)CF₂ OCF(CF₃)CF₂ O. CF(CF₃)CF₂ OCF₂ CF(CF₃)Oand CF₂ CF(CF₃)OCF(CF₃)CF₂ O linkages. The structure was confirmed by ¹⁹F NMR and elemental analysis:

¹⁹ F NMR (δ ppm vs CFCl₃): -47.6: CF₃ O; -54.0: CF₂ O; -80.0: CF(CF₃)CF₂O; -82 to -87: CF(CF₃)CF₂ O; -140 to -150: CF(CF₃)CF₂ O.

EXAMPLE 37

A mixture of 300 g tripropylene glycol methyl ether (6.46 mol), 33.7 gparaformaldehyde (1.12 mol), 150 ml benzene and 3 g ion exchange resinwas refluxed for 6 hours in a 1 liter flask equipped with a waterseparator and reflux condenser. Filtration of the product followed byvacuum distillation of the lights gave 166 g of a product with a boilingpoint above i50ec at 0.05 mm Hg.

Fluorination of 145 g of the material, dissolved in 450 ml1,1,2-trichlorotrifluoroethane, in a stirred fluorination reactorcontaining 6 liters of 1,1,2-trichlorotrifluoroethane and 700 g ofsodium fluoride gave 244 g of a fluorocarbon product in a 20 hourreaction at -3° C. Distillation of the product gave 180 g of theperfluorinated fluid: ##STR22## where the hexafluoropropylene oxideunits are attached randomly in a head to head, head to tail and tail totail fashion.

¹⁹ F NMR (δ ppm vs CFCl₃):-47.3, -56.0: CF₂ O; 54.0: CF₂ O; -80.0CF(CF₃)CF₂ O;-83.0, 85.3: CF(CF₃)CF₂ O: -145.3, -146.0: CF(CF₃)CF₂ O.

b.p. 260.0° C.

EXAMPLE 38

A mixture of 400 g dipropylene glycol (3.0 mol), 358 g paraformaldehyde(12 mol), 150 ml toluene and 10 g ion exchange resin was refluxed for 5hours in a stirred 1 liter flask equipped with a water separator. Theion exchange resin was removed prior to distillation of the mixture to150° C. under a full vacuum to remove any low molecular weight polymer.Approximately 200 g of polymer remained in the flask which was shown bygel permeation chromatography to have an average molecular weight ofapproximately 3000.

The polymer, 280 g, was mixed with 340 ml 1,1,2-trichlorotrifluoroethaneand was slowly pumped into a 15 liter stirred reactor over a 24 hourperiod. The reactor, which contained 5.5 liters of1,1,2-trichlorotrifluoroethane and 1220 g sodium fluoride powder, wasmaintained at 10° C. throughout the reaction while 20% fluorine wasbubbled through the liquid fluorination medium at a rate just exceedingthat required to react with all of the starting material being pumpedinto the reactor. The reactor contents were filtered and distilled togive 587 g of fluid which was further treated with 50% fluorine at 270°C. to give a fluid which was essentially free of hydrogen. The purifiedproduct as fractionated into three samples. The first fraction boiledbelow 200° C. at 0.05 mm Hg, the second distilled over between 200° and300° C. at 0.05 mm and the distillation bottoms had a boiling pointabove 300° C. at 0.05 mm Hg. The second fraction comprised approximately20% of the total fluid with the majority of the sample having a boilingpoint below 200° C. at 0.05 mm. The second fraction had an averagemolecular weight of 2500 by ¹⁹ F NMR.

The viscosity of the second fraction at 20° C. was 72.2 cst. (ASTM slopeof 0.644). The pour point was -62° C.

¹⁹ F NMR (δ ppm vs CFCl₃): -47.3, -49.3, -51.4: CF₂ O; -54.0. -55.8: CF₃O; -79.7: OCF(CF₃)CF₂ O; -81.8, -82.8, -84.7: OCF(CF₂)CF₂ O; -87.3: CF₃CF₂ O; -130.0: CF₃ CF₂ O; -140.3, -144.8, -146.0: CF₂ CF(CF₃)O.

Anal. Calcd. for CF₃ O CF₂ CF(CF₃)OCF₂ CF(CF₃)OCF₂ O!_(n) CF₂ CF₃ : C,21.02; F. 67.02. Found. C, 21.08; F, 67.08.

EXAMPLE 39

A mixture of 600 g 1,5-pentanediol and 30 g potassium hydroxide washeated to 160° C. in a 1 liter flask. Acetylene gas was bubbled throughthe solution as it was rapidly stirred. The reaction was stopped after40 hours and the product was washed with water and distilled to give an85% yield of pentanediol divinyl ether (b.p. 192° C.)

A 1 liter flask cooled to -12° C. was charged with 104 g pentanediol anda trace of methane sulfonic acid. To this solution was added 156 gpentanediol divinyl ether. The solution was stirred rapidly for 2 hours.Then slowly warmed to room temperature over a 6 hour period to give aviscous polymer having viscosity of 650 cst. at 100° F.

The product from the above reaction was fluorinated in a liquid phasereactor containing 1,1,2-trichlorotrifluoroethane and a sufficientamount of fluorine to complex with all of the hydrogen fluoride formedduring the reaction. A perfluoropolyether (average molecular weight of1800) having the following structure was obtained:

    CF.sub.3 CF.sub.2 CF.sub.2 CF.sub.2 O(CF.sub.2 CF.sub.2 CF.sub.2 CF.sub.2 CF.sub.2 OCF(CF.sub.3)O).sub.n CF.sub.2 CF.sub.2 CF.sub.2 CF.sub.3

EXAMPLE 40

A mixture of 400 g triethylene glycol ethyl ether (2.24 mol), 258 gacetaldehyde diethylacetal (1.39 mol), 300 ml benzene and 10 g acidicion exchange resin was refluxed in a 1 liter stirred flask. Equippedwith a continuous extractor to remove the by-product ethanol from therefluxing benzene. The solution was refluxed for 6 hours, then filteredand placed in a rotary evaporator to remove the benzene solvent.

The product was fluorinated in a 22 liter stirred tank which contained5.7 liters of 1,1,2-trichlorotrifluoroethane and 1100 g sodium fluoridepowder. The hydrocarbon (219 g) was diluted to a volume of 700 ml with1,1,2-trichlorotrifluoroethane. The solution was slowly pumped into thefluorination reactor, which was held at -5° C., over a period of 28hours. The fluorine flow was set at a level approximately 10% higherthan that required to react with all of the organic entering thereactor. Filtration of the crude reactor product followed bydistillation yielded 224 g of a clear fluid which analyzed to be:

    CF.sub.3 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF(CF.sub.3)CF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 OCF.sub.2 CF.sub.3

¹⁹ F NMR (δ ppm vs CFCl₃): -86.5: OCF(CF₃); -87.4: CF₃ CF₂ O; -88.0: CF₃CF₂ O; -88.7: OCF₂ CF₂ O; -96.3: OCF(CF₃)O.

EXAMPLE 41

In an experiment very similar to the previous one, 400 g dipropyleneglycol monomethylether (2.70 mol) was reacted with 159.5 g acetaldehydediethylacetal (1.35 mol) in benzene with an acid catalyst. Fluorinationof 250 g of the material afforded 480 g of a perfluorinated fluid havingthe following structure:

    CF.sub.3 OCF.sub.2 CF(CF.sub.3)OCF.sub.2 CF(CF.sub.3)OCF(CF.sub.3)OCF.sub.2 CF(CF.sub.3)OCF.sub.2 CF(CF.sub.3)OCF.sub.3

EXAMPLE 42

Chloroacetaldehyde (50 to 55 wt % in water) was distilled to give afraction boiling between 87 and 92° C. A 3 liter stirred flaskcontaining 1281 g of the chloroacetaldehyde distillate was placed in aroom temperature water bath. While maintaining a temperature below 55°C., 500 ml of concentrated sulfuric acid was slowly added over a onehour period. The mixture was stirred for an additional 3 days at 53° C.,then allowed to separate into two phases. The lower phase, containingsulfuric acid, was removed with a separatory funnel while the upperphase was placed into a 3 liter flask equipped with a mechanicalstirrer. Concentrated sulfuric acid (200 ml) was carefully added to thesolution while the temperature was held below 60° C. with a water baththroughout the addition. The flask was held at 50° C. for an additional20 hours resulting in a viscous oil being formed. The polymeric productwas dissolved in 1 liter methylene chloride and the solution was washedwith water several times followed by a rinse with dilute sodiumbicarbonate solution. The organic phase was isolated, dried overmagnesium sulfate and concentrated to give a dark, viscous product (719g polychloroacetaldehyde). The product was dissolved in 450 g chloroformand 305 g 1,1,2-trichlorotrifluoroethane to give a solution which wasmetered over a 22 hour period into a 20° C. fluorination reactorcontaining 5.5 liters of 1,1,2-trichlorotrifluoroethane. Following thereaction, the solvent was removed leaving behind a fluid with thefollowing structure having an average molecular weight of 850:

    ______________________________________                                         ##STR23##                                                                    Temp. °F.                                                                           Viscosity (cst.)                                                 ______________________________________                                        -65          1240                                                             100          2.53                                                             176          1.14                                                             ______________________________________                                    

EXAMPLE 43

Butoxyethoxyethanol (400 g, 2.47 mol) was reacted with 130 g polymericchloroacetaldehyde in 150 ml benzene to give a fluid which distilled at190° C. at approximately 1 torr. The product (266 g) was mixed with 500ml 1,1,2-trichlorotrifluoroethane and pumped into a 15 literfluorination reactor containing 5.7 liters1,1,2-trichlorotrifluoroethane and 1150 g sodium fluoride powder.Fluorine, diluted with approximately four volumes of nitrogen, wasmetered into the 0° C. reactor at a rate approximately 10% greater thanthat required to react stoichiometrically with the polyether. Theorganic feed rate was set to allow complete addition in approximately 23hours. Filtration of the product and removal of the1,1,2-trichlorotrifluoroethane via a distillation gave a fluorocarbonproduct which was further purified by a 12 hour fluorination at 200° C.with 40% fluorine. Approximately 520 g of fluid was recovered withapproximately 50% being the target material.

    CF.sub.3 CF.sub.2 CF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF(CF.sub.2 Cl)OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 OCF.sub.2 CF.sub.2 CF.sub.2 CF.sub.3

b.p. 245.5° C.

¹⁹ F NMR (δ ppm vs CFCl₃) -73.3: OCF(CF₂ Cl)O; -81.7: CF₃ CF₂ CF₂ CF₂ O;-83.3: CF₃ CF₂ CF₂ O; -88.0 and -88.7: OCF₂ CF₂ O; -96.7: OCF(CF₂ Cl)O;-126.5: CF₃ CF₂ CF₂ CF₂ O.

EXAMPLE 44

Chloroacetaldehyde dimethyl acetal (124 g, 1 mol),1,3-dichloro-2-propanol (258 g, 2 mol) and 5 g ion exchange resin weremixed in a 1 liter stirred flask. The mixture was heated to allow themethanol formed in the reaction to slowly distill from the flask.Approximately 70 ml of methanol was recovered over a 6 hour period. Theremaining solution was vacuum-distilled and the fraction (120 g, 38%yield) boiling between 100° C. and 145° C. at 2 mm Hg was collected. Thefluid was shown by ¹⁹ F NMR and elemental analysis to have the followingstructure: ##STR24##

The above acetal (210 g) diluted with a small amount of chloroform and1,1,2-trichlorotrifluoroethane was metered over a 14 hour period into a22° C. fluorination reactor containing 5.7 liters of1,1,2-trichlorotrifluoroethane. The crude product was further treatedwith 30% fluorine at 200° C. for several hours to give 197 g (57% yield)of clear fluid: ##STR25##

b.p.: 202° C.

¹⁹ F NMR (δ ppm vs CFCl₃): -64.5 and -65.0(a), -71.0(d), -86.7(c) and-133.7(b) ##STR26##

EXAMPLE 45

Into a 1 liter stirred flask containing 300 ml benzene were placed 516 g1,3-dichloro-2-propanol (4 mol), 120 g paraformaldehyde (4 mol) and 10 gion exchange resin. The mixture was refluxed as the water formed duringthe reaction was continuously removed. After refluxing for 6 hours, thereaction mixture was filtered and vacuum-distilled to give 354 g of aproduct with the following structure:

    (ClCH.sub.2).sub.2 CHOCH.sub.2 OCH(CH.sub.2 Cl).sub.2

b.p.: 141° C./0.05 mm Hg.

The above acetal (354 g) was mixed with 70 g chloroform and 360 g1,1,2-trichlorotrifluoroethane and fluorinated over a 24 hour period at20° C. using the procedure described in the previous example. Thereaction product was concentrated and the crude product was furthertreated with fluorine at 200° C. to give 430 g of a clear fluid (69%yield) having a boiling point of 178° C.

¹⁹ F NMR (δ ppm vs CFCl₃): -45.5(c), -65.3(a) and -137.1(b) ##STR27##

EXAMPLE 46

A mixture of 600 ml ethoxyethanol, 200 g epichlorohydrin and 10 g ionexchange resin was heated to 130° C. for 20 hours. The reaction mixturewas then cooled, filtered and distilled to give 250 g of product whichwas then reacted with 116 g paraformaldehyde to give 266 g of a productboiling above 150° C. at 0.01 mm Hg.

Fluorination of 261 g of the product in a reactor containing 5 liters of1,1,2-trichlorotrifluoroethane and 1000 g sodium fluoride gave 446 g ofperfluorinated fluid of which approximately 70% had the followingstructure: ##STR28##

b.p. 224° C.

¹⁹ F NMR (δ ppm vs CFCl₃): -46.4(h), -67.6(g), -80.9(e), -87.6(a),-89.0(b,c,d), and -141.8(f) ##STR29##

EXAMPLE 47

A mixture consisting of 100 g 2-chloroethanol (12.4 mol), 573 gepichlorohydrin (6.2 mol) and 20 g of an acidic ion exchange resin wasrefluxed for 24 hours. The mixture was then filtered to remove the ionexchange resin and the excess alcohol and unreacted epichlorohydrin wereremoved by distillation. The residue was distilled under vacuum and theproduct 1-chloro-3-(2-chloroethoxy)-2-propanol (804 g, 75% yield)distilled between 89 and 91° C. at 0.05 mm Hg.

Into a 1-liter stirred flask were placed 346 g1-chloro-3-(2-chloroethoxy)-2-propanol (2 mol), 90 g paraformaldehyde (3mol), 10 g ion exchange resin and 300 ml benzene. The mixture wasrefluxed for four hours as the water formed during the reaction wasremoved. The reaction mixture was filtered and distilled to give 267 gof a product (75% yield) with the following structure: ##STR30##

Fluorination of the product (660 g) in a typical reaction at 20° C. gave1086 g of a product (82% yield) having the following structure:##STR31##

b.p.: 223° C.

¹⁹ F NMR: (δ ppm vs CFCl₃): -46.3(f), -67.3(e), -74.3(a), -81.0(c),-87.3(b) and -141.9(d) ##STR32##

EXAMPLE 48

Into a 1 liter flask were charged 300 g trichloropentaerythritol, (1.58mol), 150 ml of benzene, 10 g ion exchange resin and 60 gparaformaldehyde (2 mol). The mixture was refluxed as water was beingremoved continuously.

A portion of the above product, 192 g, was diluted with1,1,2-trichlorotrifluoroethane to give 210 ml of solution which waspumped into a 22° C. reactor containing 4.3 liters of1,1,2-trichlorotrifluoroethane. The reaction was complete inapproximately 8 hours. The unreacted fluorine was flushed from thereactor with nitrogen gas and the product (307 g, 87.8% yield) wasrecovered by distillation:

¹⁹ F NMR (δ ppm vs CFCl₃): -48.9(a), -51.1(c), -66.4(b) ##STR33##

EXAMPLE 49

A mixture of 392 g 1,4 cylcohexanedimethanol (2.72 mol), 140 gparaformaldehyde (4.7 mol), 200 ml benzene and 10 g of a H⁺ ion exchangeresin was refluxed for several hours in a flask containing a waterseparator. A nearly quantitative yield of a sticky solid was obtainedafter removal of the solvent by distillation.

Fluorination of 263 g of the polymer, diluted with 220 g chloroform and340 g 1,1,2-trichlorotrifluoroethane in a reactor (10° C.) containing4.8 liters 1,1,2-trichlorotrifluoroethane and 1300 g sodium fluoridepower, gave 440 g of a perfluoropolyether having the followingstructure: ##STR34##

EXAMPLE 50

Into a 1 liter flask were placed 350 g tetraethylene glycol (1.8 mol),300 ml benzene, and 10 g ion exchange resin. The mixture was refluxedfor 1 hour to remove any moisture present. To the mixture was added 200ml dimethoxypropane. The distillate was continuously removed over a2-hour period in 50 ml increments, which were extracted with water toremove the ethanol formed in the reaction. After drying, the distillatewas returned to the flask. An additional 200 ml dimethoxypropane wasadded and the distillate was collected, extracted, dried, and returnedto the flask for an additional 3 hours. Removal of the resin and solventyielded 410 g of a polymeric fluid having a viscosity of 560 cst. at 30°C.

Fluorination of 336 grams of the polyether in a 10° C. reactorcontaining 5 liters of 1,1,2-trichlorotrifluoroethane and 1420 g sodiumfluoride powder gave 642 g of a perfluoropolyether having an averagemolecular weight of 1700 (69.8% yield). ##STR35##

EXAMPLE 51

A mixture of 300 g pentanediol (2.88 mol), 450 gchloroacetaldehyde/water mixture having a boiling point between 87° and92° C. and 150 ml benzene was refluxed in a flask containing a waterseparator. Approximately 5 grams of an acidic ion exchange resin wasadded to catalyze the reaction. After refluxing for approximately fivehours the solution was filtered and the benzene was removed bydistillation to leave a residue (approximately 400 g) having a viscosityof 9,700 cst. at 100° F.

Fluorination of 318 g of the polymer, diluted with 235 g chloroform and375 g 1,1,2-trichlorotrifluoroethane, in a 12° C. reactor containing 5liters of 1,1,2-trichlorotrifluoroethane and 1200 g sodium fluoridepowder gave 623 g (84% yield) of the fluorinated polyether (averagemolecular weight of 2100) in a 22-hour reaction. ##STR36##

EXAMPLE 52

A ten-liter stirred tank reactor was filled with 5.5 liters1,1,2-trichlorotrifluoroethane. 220.3 grams of phenanthrene was placedin a one-liter brass tube fitted with a plug of copper turnings in eachend of the tube and then filled with 1,1,2-trichlorotrifluoroethane.This brass tube was then placed in the liquid return line of thecondenser so that the 1,1,2-trichlorotrifluoroethane condensed in thecondenser would flow through the brass tube and dissolve somephenanthrene before entering the reactor. The fluorine flow was set at470 cc/min and the nitrogen flow was set at two liters per minute. Thereactor temperature and the brass tube containing the phenanthrene wereboth held at 19° C. during the reaction. After 20 hours, the fluorinewas stopped and the reactor was dumped. In the brass tube, 21.8 grams ofphenanthrene remained so a total of 198.5 grams had reacted. From thereactor, after removal of the 1,1,2-trichlorotrifluoroethane, a paleyellow liquid was recovered. This material was then reacted with 40cc/min fluorine and 100 cc/min nitrogen in an unstirred reactor wherethe fluorine was bubbled through the liquid at 200° C. for 12 hours togive a clear, colorless liquid. This liquid was then distilled to give517 g (74.2%) of perfluorotetradecahydrophenanthrene (b.p. 215° C.)along with 128 grams of a clear, colorless solid that melted atapproximately 60° C. and was much less volatile than theperfluorotetradecahydrophenanthrene.

EXAMPLE 53

5.3 liters 1,1,2-trichlorotrifluoroethane were placed in a ten-literstirred tank reactor. 256 grams of kerosene was diluted to 650 ml with1,1,2-trichlorotrifluoroethane. The fluorine flow was set at 650 cc/minwith the nitrogen flow at 2 liters per minute. After three minutes thekerosene solution was added at 25 ml/hr to the reactor and the reactionwas continued under these conditions while holding the reactortemperature at about 10° C. After 26 hours, all of the kerosene had beenadded and the fluorine flow was stopped fifteen minutes later. Theproduct was distilled to remove the 1,1,2-trichlorotrifluoroethane andany other material with a boiling point below about 100° C. 575 grams ofa clear, colorless liquid product was obtained after treatment with 30cc/min fluorine and 60 cc/min N₂ at 150° C. for 15 hours.

EXAMPLE 54

A ten-liter stirred tank reactor was loaded with 3.3 liters1,1,2-trichlorotrifluoroethane. 120 grams of heavy-mineral oil wasdiluted to 480 ml with 1,1,2-trichlorotrifluoroethane. The fluorine flowwas set at 350 cc/min with a nitrogen flow of 1.5 liters per minute. Themineral oil was added to the reactor at a rate of 20 ml/hr. After 24hours, the reaction was complete and the reactor was dumped. Afterremoval of the 1,1,2-trichlorotrifluoroethane, 385 grams of product wasobtained.

This product was then treated with 30 cc/min fluorine and 60 cc/minnitrogen at 200° C. for 16 hours to give 306 grams of a soft paste thatbecame a completely clear, colorless liquid at approximately 80° C.

EXAMPLE 55

A ten-liter stirred tank reactor was loaded with five liters of1,1,2-trichlorotrifluoroethane. 202 grams of Amoco Indopol™ H-100polybutene (MW 920) was diluted to 610 ml with1,1,2-trichlorotrifluoroethane. The fluorine flow was set at 460 cc/minwith a nitrogen flow of 1.5 liters per minute. The polybutene was thenadded at a rate of 25 ml/hr while the reactor was held at -3° C. Onceall the polybutene had been added (24 hours), the fluorine was reducedto 300 cc/min and the nitrogen reduced to 1.2 liters per minute andthese conditions were maintained for 15 minutes after which the fluorineflow was stopped and the reactor was dumped. After removal of the1,1,2-trichlorotrifluoroethane, the product was placed in a 600 mlbeaker on a hot plate in a fume hood for eight hours at approximately120° C. to remove any light fraction in the oil. 496 grams of a viscous,colorless, slippery oil was obtained that has a pour point of about -15°C. and an average molecular weight of 1500.

EXAMPLE 56

A ten-liter stirred tank reactor was loaded with 5.0 liters1,1,2-trichlorotrifluoroethane. 216 grams of Uniroyal Chemical'sTrilene™ CP80 ethylene propylene copolymer (molecular weightapproximately 8000) was diluted in 1,1,2-trichlorotrifluoroethane togive 800 ml. The fluorine flow was started at 420 cc/min and thenitrogen flow was at 1.6 liters/minute. After a few minutes, the CP80solution was added at 25 ml/hr while the reactor was held at 10° C.After 31 hours, all of the CP80 had been added but the fluorineconcentration in the gas outlet line rose only slowly. After one hour,the fluorine flow was reduced to 200 cc/min with a nitrogen flow of 800cc/min and the conditions were held for five hours after which time thefluorine flow was stopped. When the reactor was dumped, a gelatinousproduct was obtained that was insoluble in the1,1,2-trichlorotrifluoroethane. When all of the1,1,2-trichlorotrifluoroethane was removed from the gelatinous product,680 grams of somewhat brittle white solid was left. A small portion ofthis solid was ground into a powder and 20 grams was placed in aone-foot-long copper boat. This copper boat was placed in a 1"×18"nickel tube and exposed to pure fluorine at 85° C. for 20 hours (5cc/min F₂ flaw). When this was done there was 20.6 grams of a veryviscous, clear, colorless elastomer in the boat which was insoluble in1,1,2-trichlorotrifluoroethane and all other solvents tried.

EXAMPLE 57

A ten-liter stirred tank reactor was loaded with 5.0 liters1,1,2-trichlorotrifluoroethane. 275 grams of poly(alpha-methylstyrene)(having an average molecular weight of 685) was dissolved in 400 gchloroform and 400 g 1,1,2-trichlorotrifluoroethane to give about 800ml. The fluorine flow was set at 350 cc/min and the nitrogen flow wasset at 1400 cc/min. The poly(alpha-methylstyrene) solution was added ata rate of 20 ml/hr while the reactor temperature was held at 12° C.After 39 hours, all of the poly-(alpha-methylstyrene) solution had beenadded and the fluorine flow was left on for one more hour. When thereactor was dumped, a pale yellow solution was recovered which containedapproximately one gram of insoluble white powder. The solution wasfiltered and the 1,1,2-trichlorotrifluoroethane was removed bydistillation to give 785 grams of a pale yellow, somewhat brittle solidthat melted at about 50° C. The melting point of the solid could beraised by distilling some of the low molecular weight product out of thesolid. Approximately one third of the product boiled below 175° C. at 1torr.

EXAMPLE 58

3.7 liters 1,1,2-trichlorotrifluoroethane were placed in a ten-literstirred tank reactor. 69 g tri-n-hexylamine and 54 g trifluoroaceticacid were diluted in 1,1,2-trichlorotrifluoroethane to give 300 ml. Thefluorine flow was set at 400 cc/min and the nitrogen flow was set at1600 cc/min. The trihexylamine was added at 35 ml/hr while the reactorwas maintained at 22° C. When all of the amine had been added (8 hours),the fluorine flow was reduced to 100 cc/min with the nitrogen at 800cc/min. These conditions were maintained for four hours after which timethe fluorine was turned off and the reactor was dumped. The productconsisted of a colorless liquid with a thick, brown tar floating on topand coating the walls of the reactor. The soluble phase contained 71grams of perfluorotrihexylamine (37%).

EXAMPLE 59

Into a 1 liter stirred flask were placed 350 g 1,5 pentanediol (3.4mol), 23 g n-butanol (0.3 mol), 175 g paraformaldehyde (5.8 mol) and 200ml benzene. Upon refluxing the mixture for approximately 3 hours with anacid catalyst present, 390 g of a polymeric fluid was obtained which hada viscosity of 450 cst. at 100° F. Fluorination of 310 g of the fluid ina typical fluorination reaction at 14° C. gave 708 g of fluid (80%yield) of which approximately 30% boiled between 200° and 300° C. at0.05 mm Hg. The average molecular weight was 2800. ##STR37##

EXAMPLE 60

Using techniques similar to those described in the previous examples,350 g 1,6-hexanediol (3.0 mol) 49.3 g n-pentanol (0.56 mol), 134 gparaformaldehyde (4.46 mol) were reacted in benzene to give 425 g of apolymeric material having a viscosity of 600 cst. at 100° F.Fluorination of 628 g of the fluid in a typical reaction at 10° C. gave628 g of fluid (71% yield), of which approximately 30% boiled between200° and 300° C. at 0.05 mm Hg. ##STR38##

EXAMPLE 61

A mixture of 600 g diethylene glycol and 30 g potassium hydroxide washeated to 160° C. in a 1 liter flask. Acetylene gas was bubbled throughthe solution as it was rapidly stirred. The reaction was stopped after48 hours and the product was extracted with water several times toremove any unreacted diethylene glycol. The product, a divinyl ether ofdiethylene glycol, was recovered by distillation (b.p. 196° C.) in aboutan 80% yield.

A liter flask cooled to -10° C. was charged with 250 g triethyleneglycol ethyl ether and a catalytic amount of methane sulfonic acid. Tothis solution was added slowly 100 g diethylene divinyl ether. Followingthe addition, the flask was slowly warmed to room temperature over a 3hour period. The product was distilled to 150° C. at 0.05 mm Hg toremove any unreacted starting materials.

The product from the above reaction can be fluorinated at 20° C. usingthe procedures outlined in the previous liquid phase fluorinationexamples to give a perfluorinated fluid of the following structure:

    CF.sub.3 CF.sub.2 O(CF.sub.2 CF.sub.2 O).sub.3 CF(CF.sub.3)O(CF.sub.2 CF.sub.2 O).sub.2 CF(CF.sub.3)O(CF.sub.2 CF.sub.2 O)CF.sub.2 CF.sub.3

C₂₄ F₅₀ O₁₁

b.p. 300° C.

EXAMPLE 62

A mixture of 300 g 1-propanol (5.0 mol), 231 g epichlorohydrin and 10 gion exchange resin was refluxed for 22 hours. The reaction mixture wasthen cooled, filtered and distilled to give 281 g of1-chloro-3-propoxy-2-propanol (74% yield). Reaction of this product withparaformaldehyde (2.8 mol) gave 202 g of product (69% yield) having thefollowing structure: ##STR39##

Fluorination of the above acetal in a 23 hour reaction at 20° C. gave404 g or product (81% yield) having the following structure: ##STR40##

EXAMPLE 63

Eighty grams of diethoxymethane were fluorinated in a 4-liter stirredtank reactor containing 1.5 liters (CF₂ Cl)₂ CFOCF₂ OCF(CF₂ Cl)₂ as afluorination solvent and 400 g sodium fluoride powder. Thediethoxymethane, diluted with 200 ml of (CF₂ Cl)₂ CFOCF₂ OCF(CF₂ Cl)₂,was pumped into the reactor over an 18 hour period. Fluorination of thefluid at 10° C. with 30% fluorine gave a 90% yield of a product having aboiling point of 92.5° C. The product was obtained in greater than 99%purity following an atmospheric distillation.

¹⁹ F NMR (84.87 MHz, CFCl₃) -52.4(pentet, c), -87.3 (singlet, a),-90.1(triplet, b). ##STR41##

EXAMPLE 64

A mixture consisting of 500 g 2-chloroethanol (6.25 moles), 120 gparaformaldehyde (4 moles), 5 g of an acidic ion exchange resin and 100ml benzene was refluxed for several hours. The water formed during thereaction was continuously removed. The mixture was filtered to removethe ion exchange resin and the unreacted 2-chloroethanol and benzenewere removed by distillation. The residue was distilled to givebis(2-chloroethoxy)methane in a nearly quantitative yield. One hundredtwenty grams of the product was fluorinated in a 4 liter stirred reactorcontaining 1.5 liters (CF₂ Cl)₂ CFOCF₂ OCF(CF₂ Cl)₂ in a 30 hourreaction at 20° C. to give a 92% yield of perfluorobis(2-chloroethoxy)methane!. The product (b.p. 92.5° C.) was obtained ingreater than 99% yield by distillation.

¹⁹ F NMR (84.87 MHz, CFCl₃) -52.1 (pentet, c), -74.0 (singlet, a), -88.8(triplet, b). ##STR42##

EXAMPLE 65

The reaction of 500 g dimethoxymethane (6.6 moles) with 100 g1,3-dioxolane (1.4 moles), in the presence of an acidic catalyst, gave amixture of unreacted dimethoxymethane, low molecular weight oligomers of1,3-dioxolane and a product having the formula: CH₃ OCH₂ OCH₂ CH₂ OCH₂OCH₃ which was isolated in 50% yield. Fluorination of 80 g of theproduct in a 4 liter reactor containing 1.5 liters (CF₂ Cl)₂ CFOCF₂OCF(CF₂ Cl)₂ and 400 g sodium fluoride in an 18 hour reaction at 10° C.,gave a 60% yield of perfluoro-2,4,7,9-tetraoxadecane (b.p. 79.0° C.).

¹⁹ F NMR (84.87 MHz, CFCl₃) -54.1 (pentet, b) -57.7 (triplet, a), -90.9(triplet, c). ##STR43##

EXAMPLE 66

3,5,7-trioxanonane was prepared in low yield by reaction of 500 gethanol (10.9 moles) with 500 g paraformaldehyde (16.7 moles) in 200 mlof benzene containing 5 g of an acidic ion exchange resin. The reactionwas done in a 2 liter flask equipped with a water separator and refluxcondenser. The major product formed, diethoxymethane, was removed fromthe product mixture along with the benzene by distillation. Theremaining residue contained low molecular weight oligomers offormaldehyde having the general formula: CH₃ CH₂ (OCH₂)_(n) OCH₂ CH₃.The primary component, CH₃ CH₂ OCH₂ OCH₂ OCH₂ CH₃ was isolated in abouta 10% yield. Fluorination of the product in (CF₂ Cl)₂ CFOCF₂ OCF(CF₂Cl)₂ containing sodium fluoride gave a 45% yield ofperfluoro-3,5,7-trioxanonane.

¹⁹ F NMR (84.87 MHz, CFCl₃) -53.7 (multiplet, c) -87.4 (singlet, a),-90.6 (triplet, b). ##STR44##

EXAMPLE 67

Eighty grams of acetaldehyde diethyl acetal were fluorinated in 20 hourreaction using a fluorine flow rate of 250 cc/min. The hydrocarbon wasslowly pumped into a reactor containing 1.5 liters (CF₂ Cl)₂ CFOCF₂OCF(CF₂ Cl)₂ and 400 g sodium fluoride. The product, was obtained in a45% yield and in 98% purity after distillation.

¹⁹ F NMR (84.87 MHz, CFC₃) -86.7 (multiplet, d), -87.5 (singlet, a),-88.1 (multiplet, b), -97.0 (pentet, c). ##STR45##

EXAMPLE 68

Eighty grams of triethyl orthoformate were fluorinated in a 4-literstirred tank reactor containing 1.5 liters (CF₂ Cl)₂ CFOCF₂ OCF(CF₂ Cl)₂and 400 g sodium fluoride powder. The triethyl orthoformate, dilutedwith 200 ml (CF₂ C)₂ CFOCF₂ OCF(CF₂ Cl)₂ was pumped into the reactorover an 18 hour period. Fluorination of the fluid at 10° C. with 30%fluorine gave a 55% yield of a product having a boiling point of 92.5°C. The product was obtained in greater than 99% purity following anatmosphic distillation.

¹⁹ F NMR (84.87 MHz, CFCl₃) -52.2 (septet, c), -87.6 (singlet, a) -90.7(doublet, b). ##STR46##

EXAMPLE 69

A mixture of 3,612 g butoxyethanol (30.6 moles), 261 g paraformaldehyde(8.7 moles), 5 g ion exchange resin and 350 ml toluene was stirred atreflux as the water formed in the reaction was continuously removed.After 5 hours, the reaction was complete and a nearly quantitative yieldof bis(2-butoxyethoxy)methane, bp 100°-110° C. at 0.5 Torr, wasrecovered. 915 g of bis(2-butoxyethoxy)methane was diluted to a volumeof 1700 ml with 1,1,2-trichlorotrifluoroethane and pumped into a 5 literreactor containing 5.7 liters of 1,1,2-trichlorotrifluoroethane. Thereaction, which was carried out at 23° C., was complete in approximately72 hours. The product, perfluorobis(2-butoxyethoxy)methane was obtainedin 62% yield.

¹⁹ F NMR (δ ppm vs CFCl₃) -51.7 (f), -81.6 (a), -83.4 c), -88.7 (e),-90.5 (d), -126.5 (b) ##STR47##

EXAMPLE 70

A 4 liter stirred reactor was charged with 2 liters Fluorinert FC-75 (3MCorporation; mixture of perfluoro(2-n-butyltetrahydrofuran) andperfluoro(2-n-propyltetrahydropyran)) and heated to 70° C. Eighty gramsof bis(2-butoxyethoxy)methane was pumped into the reactor neat over an18 hour period. The product, perfluorobis(2-butoxyethoxy)methane, wasrecovered in 41% yield following an atmosphoric distillation (b.p. 178°C.). The ¹⁹ F NMR was identical to that obtained when the product wasprepared in 1,1,2-trichlorotrifluoroethane as the fluorination solvent(previous example).

Equivalents

Those skilled in the art will recognize or be able to ascertain using nomore than routine experimentation many equivalents to the specificembodiments of the invention described herein. Such equivalents areintended to be encompassed by the following claims.

We claim:
 1. A fluorination method for replacing essentially all of the hydrogen atoms of a hydrogen-containing compound with fluorine atoms, comprising the steps of:a) introducing fluorine gas into an inert liquid medium, wherein a turbulent inert liquid medium is established; b) introducing the hydrogen-containing compound into the turbulent inert liquid medium so that the hydrogen-containing compound is dissolved or dispersed within the turbulent inert liquid medium; c) fluorinating the hydrogen-containing compound present in the turbulent inert liquid medium under fluorination conditions, the fluorination conditions being sufficient to replace hydrogen atoms in the hydrogen-containing compound with fluorine atoms and wherein the fluorine gas is in a concentration low enough so that the vapor of the inert liquid medium and fluorine do not form a flammable mixture at the fluorination conditions; and d) continuing the introduction of fluorine gas under the fluorination conditions until essentially all of the hydrogen atoms of the hydrogen-containing compound have been replaced with fluorine atoms without substantial oligomerization and/or polymerization of the hydrogen-containing compound.
 2. The method of claim 1 wherein the fluorine gas is introduced with an inert gas.
 3. The method of claim 2 wherein the inert gas includes nitrogen gas.
 4. The method of claim 1 wherein the hydrogen-containing compound includes an ether or polyether having 5 to 10,000 carbon atoms.
 5. The method of claim 1 wherein the inert liquid medium includes a perfluorocarbon, chlorofluorocarbon or chlorofluoroether.
 6. The method of claim 5 wherein the inert liquid medium includes 1,1,2-trichlorotrifluoroethane.
 7. The method of claim 1 wherein the inert liquid medium includes a perhalogenated chlorofluoropolyether.
 8. The method of claim 7 wherein the perhalogenated chlorofluoropolyether is selected from the group consisting of (CF₂ Cl)₂ CFOCF₂ OCF(CF₂ Cl)₂ and CF₂ ClCF₂ OCF₂ OCF₂ CF₂ Cl.
 9. The method of claim 1 wherein the hydrogen-containing compound is first dissolved in a solvent and is then introduced into the inert liquid medium in solution.
 10. The method of claim 9 wherein the solvent includes the inert liquid medium.
 11. The method of claim 1 wherein the hydrogen-containing compound is insoluble in the inert liquid medium and is introduced into the inert liquid medium to form a suspension or emulsion.
 12. The method of claim 1 wherein the emulsion or suspension is formed continuously as the fluorination reaction proceeds.
 13. The method of claim 1 wherein the fluorination is carried out at a temperature in the range of between about -40° and 150° C.
 14. The method of claim 1 wherein the fluorination is carried out at a temperature in the range of between about -40° and 90° C.
 15. The method of claim 1 wherein the fluorination is carried out at a temperature in the range of between about -10° and 50° C.
 16. The method of claim 1 wherein the fluorination is carried out in the presence of a hydrogen fluoride scavenger.
 17. The method of claim 16 wherein the hydrogen fluoride scavenger includes sodium fluoride.
 18. The method of claim 1 wherein the gaseous products of the fluorination are circulated through a bed containing a hydrogen fluoride scavenger and then are reintroduced back into the inert liquid medium.
 19. The method of claim 18 wherein the hydrogen fluoride scavenger includes sodium fluoride.
 20. The method of claim 1 wherein the hydrogen-containing compound is disposed in an organic feed container and a portion of the inert liquid medium is directed into the organic feed container, wherein the hydrogen-containing compound is then mixed with the extracted portion of the inert liquid medium and both are returned to the inert liquid medium to introduce the hydrogen-containing compound.
 21. A method for replacing essentially all of the hydrogen atoms of a hydrogen-containing compound by liquid-phase fluorination, comprising the steps of:a) providing a fluorination reactor, wherein the reactor comprises a reaction vessel having means for agitating a liquid contained therein, means for introducing the hydrogen-containing compound into the liquid, means for introducing a gas into the liquid, means for removing a vaporized liquid from the reaction vessel operatively linked to means for condensing the vaporized liquid, and means for returning the condensed liquid to the reaction vessel; b) introducing fluorine gas into an inert liquid medium; c) directing the hydrogen-containing compound in the inert liquid medium in the reaction vessel to form a turbulent inert liquid medium so that the hydrogen-containing compound is dispersed or dissolved within the inert liquid medium; d) fluorinating the hydrogen-containing compound, the amount of fluorine gas being in excess of the stoichiometric amount necessary to replace the hydrogen atoms in the hydrogen-containing compound and wherein the fluorine gas is in a concentration low enough so that the vapor of the inert liquid medium and fluorine do not form a flammable mixture during fluorination; and e) continuing the fluorination reaction until essentially all of the hydrogen atoms of the hydrogen-containing compound are replaced with fluorine atoms without substantial concurrent oligomerization and/or polymerization of the hydrogen-containing compound.
 22. A process for forming a perfluorinated organic compound which comprises the steps of:a) providing a reaction system comprising a reactor and a means for conveying a fluid through the reactor; b) conveying through the reactor a turbulent fluid comprising an organic compound, which can be fluorinated to from the perfluorinated organic compound, and an inert liquid medium; c) introducing fluorine gas into the turbulent fluid, the ratio of organic compound to fluorine being sufficient to obtain a chemical reaction between them; and d)fluorinating the organic compound in the turbulent fluid, wherein the fluorine gas is in a concentration low enough so that the vapor of the inert liquid medium and fluorine do not form a flammable mixture while fluorinating and for a time sufficient to yield the perfluorinated compound without substantial oligomerization and/or polymerization of the organic compound.
 23. The process of claim 22 wherein the hydrogen-containing compound is selected from the group consisting of monoethers, polyethers, alcohols, acetals, carboxylic acid esters, sulfonyl fluorides, sulfonate esters, chlorohydrocarbons, hydrocarbons and fluorohydrocarbons.
 24. The process of claim 22 wherein the fluorine is diluted with an inert gas.
 25. The process of claim 24 wherein the inert gas includes nitrogen.
 26. A fluorination method for replacing essentially all of the hydrogen atoms of a hydrogen-containing compound with fluorine atoms, comprising the steps of:a) introducing fluorine gas into an liquid medium, wherein a turbulent liquid medium is established, said liquid medium selected from the group consisting of a perfluorocarbon, chlorofluorocarbon, chlorofluoroether and a mixture of perfluoro(2-n-butyltetrahydrofuran) and perfluoro(2-n-propyltetrahydrofuran); b) introducing the hydrogen-containing compound into the turbulent liquid medium so that the hydrogen-containing compound is dissolved or dispersed within the turbulent liquid medium; c) fluorinating the hydrogen-containing compound present in the turbulent liquid medium under fluorination conditions, the fluorination conditions being sufficient to replace hydrogen atoms in the hydrogen-containing compound with fluorine atoms and the fluorine being diluted to a concentration low enough so that the vapor of the liquid medium and fluorine do not form a flammable mixture under fluorination conditions; and d) continuing the introduction of fluorine gas under the fluorination conditions until essentially all of the hydrogen atoms of the hydrogen-containing compound have been replaced with fluorine atoms without substantial oligomerization and/or polymerization of the hydrogen-containing compound.
 27. The method of claim 26 wherein the liquid medium includes 1,1,2-trichlorotrifluoroethane or a mixture of perfluoro(2-n-butyltetrahydrofuran) and perfluoro(2-n-propyltetrahydrofuran).
 28. The method of claim 26 wherein the liquid medium includes a chlorofluoropolyether or a mixture of perfluoro(2-n-butyltetrahydrofuran) and perfluoro(2-n-propyltetrahydrofuran).
 29. The method of claim 28 wherein the liquid medium includes a chlorofluoropolyether selected from the group consisting of (CF₂ Cl)₂ CFOCF₂ OCF(CF₂ Cl)₂ and CF₂ ClCF₂ OCF₂ OCF₂ CF₂ Cl or a mixture of perfluoro(2-n-butyltetrahydrofuran) and perfluoro(2-n-propyltetrahydrofuran).
 30. The method of claim 26 wherein the hydrogen-containing compound is insoluble in the liquid medium and is introduced into the liquid medium to form a suspension or emulsion.
 31. The method of claim 30 wherein the emulsion or suspension is formed continuously as the fluorination reaction proceeds.
 32. The method of claim 26 wherein the fluorination is carried out at a temperature in the range of between about -40° and 90° C.
 33. The method of claim 26 wherein the gaseous products of the fluorination are circulated through a bed containing a hydrogen fluoride scavenger and then are reintroduced back into the liquid medium.
 34. The method of claim 33 wherein the hydrogen fluoride scavenger includes sodium fluoride.
 35. The method of claim 26 wherein the hydrogen-containing compound is disposed in an organic feed container and a portion of the liquid medium is directed into the organic feed container, wherein the hydrogen-containing compound is then mixed with the extracted portion of the liquid medium and both are returned to the liquid medium to introduce the hydrogen-containing compound. 